JP5223327B2 - Lead acid battery - Google Patents
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- JP5223327B2 JP5223327B2 JP2007330671A JP2007330671A JP5223327B2 JP 5223327 B2 JP5223327 B2 JP 5223327B2 JP 2007330671 A JP2007330671 A JP 2007330671A JP 2007330671 A JP2007330671 A JP 2007330671A JP 5223327 B2 JP5223327 B2 JP 5223327B2
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- 239000002253 acid Substances 0.000 title claims description 15
- 239000011575 calcium Substances 0.000 claims description 58
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 57
- 229910052791 calcium Inorganic materials 0.000 claims description 57
- 239000011701 zinc Substances 0.000 claims description 33
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 32
- 229910052725 zinc Inorganic materials 0.000 claims description 32
- 239000007774 positive electrode material Substances 0.000 claims description 23
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 20
- 229910001424 calcium ion Inorganic materials 0.000 claims description 20
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 19
- 239000008151 electrolyte solution Substances 0.000 claims description 19
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 238000011156 evaluation Methods 0.000 description 21
- 230000000694 effects Effects 0.000 description 15
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 10
- 239000011149 active material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 238000010828 elution Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- -1 aluminum ions Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は鉛蓄電池に関するもので、さらに詳しく言えば、そのサイクル寿命特性を向上させ、長寿命化が図れる鉛蓄電池に関するものである。 The present invention relates to a lead-acid battery, and more specifically to a lead-acid battery that can improve its cycle life characteristics and extend its life.
鉛蓄電池は、低価格で安定した性能を有することから、自動車のエンジン始動用を中心とした需要が高く、近年は、放電容量が大きく、長寿命、放置時の性能向上といった高性能なものが求められており、種々の検討がなされている。 Lead-acid batteries are highly demanded mainly for automobile engine starting because of their low price and stable performance. In recent years, lead-acid batteries have high discharge capacity, long life, and improved performance when left unattended. There are demands and various studies have been made.
たとえば、正極板では負極板に比べて充放電サイクルの経過とともに活物質粒子間の結着性が低下しやすく、その結果として活物質の軟化、脱落が生じて寿命に至ることが知られていることから、鉛粉から作製したペーストを格子体に充填し、熟成、乾燥の工程を経て得られる未化成の正極活物質の主成分である三塩基性硫酸鉛を四塩基性硫酸鉛にしたものがある。このように、三塩基性硫酸鉛を四塩基性硫酸鉛にしたものでは、四塩基性硫酸鉛は粒子径が三塩基性硫酸鉛より大きく、四塩基性硫酸鉛の化成によって得られる二酸化鉛も、その粒子径が大きくなって活物質の軟化、脱落を抑制することができる。このことは特許文献１に開示されている。
また、特許文献２には、鉛粉を主成分とする正極用ペースト状活物質中に該鉛粉に対して酸化カルシウムを０．００１〜０．５質量％添加したことで、鉛蓄電池の長寿命化を図ることが開示されており、特許文献３には、カルシウムまたはカルシウムとスズを含む正極活物質を用いた正極とアルミニウムイオンを含む電解液とを組み合わせることで、活物質の導電性と密着性の向上および活物質粒子間の結着性の向上を図った鉛蓄電池が開示されている。
本発明は上記課題に鑑みてなされたもので、鉛を主成分とする正極活物質原料にカルシウム又はその化合物と亜鉛又はその化合物を添加することで、電槽化成時に正極活物質中からのカルシウムの溶出を抑制するようにしたものである。すなわち、特許文献３によれば、カルシウムを含む正極活物質は基板−活物質界面のα−ＰｂＯ2を安定化させることができ、そこにスズを併存させることで、その導電性が向上できるとあるが、電槽化成時に正極活物質中からのカルシウムが溶出するということは開示されておらず、スズにカルシウムの溶出防止の効果があることも開示されていない。 The present invention has been made in view of the above problems, and by adding calcium or a compound thereof and zinc or a compound thereof to a cathode active material material containing lead as a main component, calcium contained in the cathode active material at the time of forming a battery case. Elution is suppressed. That is, according to Patent Document 3, the positive electrode active material containing calcium can stabilize α-PbO 2 at the substrate-active material interface, and the conductivity can be improved by coexisting tin therewith. However, it is not disclosed that calcium from the positive electrode active material is eluted during the formation of the battery case, and it is not disclosed that tin has an effect of preventing calcium from being eluted.
すなわち、本発明に係る鉛蓄電池は、カルシウム又はその化合物と亜鉛又はその化合物を含有した、鉛を主成分とする正極活物質原料を含む正極板を用い、前記正極活物質原料は、０．１０質量％以上、１．２０質量％以下のカルシウムと、０．１０質量％以上、２．００質量％以下の亜鉛を含むことを特徴（請求項１）とし、さらに前記各鉛蓄電池が、マグネシウムイオンを電解液中に含有することを特徴（請求項２）とし、電解液中のカルシウムイオン又はマグネシウムイオンは、１リットル当たりの電解液量に対して０．１０ｇ以上、１０．００ｇ以下であることを特徴（請求項３）とする。 That is, the lead storage battery according to the present invention uses a positive electrode plate containing a positive electrode active material material containing lead as a main component and containing calcium or a compound thereof and zinc or a compound thereof, and the positive electrode active material material is 0.10. mass% or more, and calcium 1.20 mass% or less, 0.10 wt% or more, characterized (claim 1) comprises a 2.00 mass% of zinc, more each lead storage battery, a magnesium ion and characterized in that it contains in the electrolyte (claim 2), calcium ions or magnesium ions in the electrolyte, it 0.10g or more with respect to the amount of electrolyte per liter, or less 10.00g Is a feature (claim 3 ).
鉛を主成分とする正極活物質原料に、カルシウム又はその化合物と亜鉛又はその化合物を含有させることで、活物質中からのカルシウムの溶出を抑制することが可能となり、サイクル寿命特性の低下を抑制することができ、さらに電解液中にカルシウムイオン又はマグネシウムイオンの少なくとも一方を含有させることで、その効果を高めることができる。 By including calcium or a compound thereof and zinc or a compound thereof in the positive electrode active material material containing lead as a main component, it becomes possible to suppress the elution of calcium from the active material, thereby suppressing deterioration in cycle life characteristics. Furthermore, the effect can be heightened by containing at least one of calcium ion or magnesium ion in the electrolytic solution.
以下、本発明を、その実施形態に基づいて説明する。 Hereinafter, the present invention will be described based on the embodiments.
本発明の鉛蓄電池は、カルシウム又はその化合物と亜鉛又はその化合物を含有した、鉛を主成分とする正極活物質原料を正極板に用い、また前記鉛蓄電池が、カルシウムイオン又はマグネシウムイオンの少なくとも一方を含有させた電解液を備えてなる。 The lead acid battery of the present invention uses a positive electrode active material material containing lead as a main component and containing calcium or a compound thereof and zinc or a compound thereof as a positive electrode plate, and the lead acid battery includes at least one of calcium ions or magnesium ions. It is provided with an electrolytic solution containing.
鉛を主成分とする正極活物質原料としてはＰｂＯと金属鉛を含む、公知の方法で得られるものが使用されるが、必要に応じて、さらに、有機短繊維などの添加物が添加されることを妨げるものではない。なお、公知の方法で得られる正極活物質原料中のＰｂＯと金属鉛との比率はＰｂＯが６０〜９０質量％、金属鉛が４０〜１０質量％のものである。 As the positive electrode active material raw material containing lead as a main component, a material obtained by a known method containing PbO and metallic lead is used. If necessary, an additive such as an organic short fiber is added. It does not prevent it. In addition, the ratio of PbO and metal lead in the positive electrode active material raw material obtained by a known method is such that PbO is 60 to 90% by mass and metal lead is 40 to 10% by mass.
そして、上記正極活物質原料中に含有させる、カルシウム又はその化合物と亜鉛又はその化合物は、カルシウムが０．１０質量％以上、１．２０質量％以下であるのが好ましく、亜鉛が０．１０質量％以上、２．００質量％以下であるのが好ましい。カルシウムの含有量が１．２０質量％を超えると、溶出するカルシウムの量が増大してサイクル寿命性能の低下の原因となるからである。本発明では、カルシウムの含有量をサイクル寿命性能が低下しない程度に抑え、亜鉛を含有させることで、カルシウムの溶出を抑制するようにしている。 The calcium or compound thereof and zinc or compound thereof contained in the positive electrode active material raw material preferably have a calcium content of 0.10% by mass to 1.20% by mass, and zinc of 0.10% by mass. % Or more and 2.00% by mass or less is preferable. This is because if the calcium content exceeds 1.20% by mass, the amount of calcium to be eluted increases, causing a decrease in cycle life performance. In the present invention, the calcium content is suppressed to such an extent that the cycle life performance is not lowered, and zinc is contained to suppress calcium elution.
また、本発明では、カルシウムイオン又はマグネシウムイオンの少なくとも一方を含有させた電解液を用いることで、カルシウムの溶出抑制の効果をさらに向上させている。電解液中に含有させるカルシウムイオン又はマグネシウムイオンは１リットル当たりの電解液量に対して０．１０ｇ以上、１０．００ｇ以下であるのが好ましい。カルシウムイオン又はマグネシウムイオンの量が１リットル当たりの電解液量に対して１０．００ｇを超えると、正極活物質からのカルシウムの溶出抑制の効果よりも電解液中に含まれるカルシウムイオン又はマグネシウムイオンの増大によるサイクル寿命性能の低下の方が大きくなるからである。 Moreover, in this invention, the effect of the elution suppression of calcium is further improved by using the electrolyte solution containing at least one of calcium ion or magnesium ion. The calcium ion or magnesium ion contained in the electrolytic solution is preferably 0.10 g or more and 10.00 g or less with respect to the amount of the electrolytic solution per liter. When the amount of calcium ions or magnesium ions exceeds 10.00 g with respect to the amount of electrolyte solution per liter, the calcium ions or magnesium ions contained in the electrolyte solution are more effective than the effect of suppressing the elution of calcium from the positive electrode active material. This is because the decrease in cycle life performance due to the increase is greater.
以下、本発明を、具体的な実施例に基づいて説明する。 Hereinafter, the present invention will be described based on specific examples.
まず、公知の方法でＰｂＯと金属鉛を含む正極活物質原料としての鉛粉を作製し、次に、この鉛粉を公知の方法によってペ−ストにして、寸法が１００ｍｍ×１１５ｍｍの鋳造極板に充填して正極板を作製し、熟成、乾燥の工程を経た後、この正極板を４枚と公知の方法で作製した負極板を５枚とを交互に積層して極板群を組み立て、この極板群を所定の寸法の電槽の６つのセル内に収納して各極板群を直列に接続して１２Ｖ、２７Ａｈの鉛蓄電池とし、さらに公知の条件にて電槽化成に供して完成電池とする。このとき、正極活物質原料としての鉛粉には、以下に詳述するように、種々の質量％でカルシウム又はその化合物と亜鉛又はその化合物を含有させるが、本実施例ではカルシウムとして酸化カルシウムを含有させ、亜鉛として酸化亜鉛を含有させ、カルシウム量は正極活物質中のＣａの質量％で示し、亜鉛量は正極活物質中のＺｎの質量％で示した。 First, lead powder as a positive electrode active material raw material containing PbO and metallic lead is prepared by a known method, and then this lead powder is paste by a known method to obtain a cast electrode plate having a size of 100 mm × 115 mm. After the aging and drying steps, 4 positive electrode plates and 5 negative electrode plates produced by a known method are alternately stacked to assemble the electrode plate group. This electrode plate group is housed in six cells of a battery case of a predetermined size, and each electrode plate group is connected in series to form a lead-acid battery of 12V, 27 Ah, and further subjected to battery case formation under known conditions. Completed battery. At this time, the lead powder as the positive electrode active material raw material contains calcium or a compound thereof and zinc or a compound thereof in various mass% as described in detail below. In this embodiment, calcium oxide is used as calcium. Zinc oxide was contained as zinc, the amount of calcium was shown by mass% of Ca in the positive electrode active material, and the amount of zinc was shown by mass% of Zn in the positive electrode active material.
（評価試験１）
鉛粉中にカルシウムのみを０．０５質量％、０．１０質量％、０．２０質量％、０．５０質量％、１．００質量％、１．２０質量％、１．５０質量％、２．００質量％添加した正極板を用いた比較例１〜８に係る鉛蓄電池と、カルシウムを添加しない正極板とを用いた従来例に係る鉛蓄電池とを作製し、電槽化成時に電解液中に溶出したカルシウムの量を原子吸光法によって測定することで、正極板中に残存するカルシウムの量を測定するとともに、２５℃、５時間率定電流で充放電サイクル寿命試験に供し、従来例に係る鉛蓄電池の寿命時のサイクル数（寿命サイクル比）を１．００として、比較例１〜８に係る鉛蓄電池の寿命サイクル比を求め、結果を表１に示す。
(Evaluation Test 1)
0.05%, 0.10%, 0.20%, 0.50%, 1.00%, 1.20%, 1.50%, 2% calcium alone in lead powder A lead storage battery according to Comparative Examples 1 to 8 using a positive electrode plate added with 0.00 mass% and a lead storage battery according to a conventional example using a positive electrode plate to which calcium is not added are produced, and the electrolyte solution is formed in the electrolytic solution at the time of forming the battery case. In addition to measuring the amount of calcium remaining in the positive electrode plate by measuring the amount of calcium eluted into the positive electrode plate, it was subjected to a charge / discharge cycle life test at 25 ° C. and a constant current rate of 5 hours. The number of cycles (life cycle ratio) at the time of the life of the lead storage battery is set to 1.00, the life cycle ratio of the lead storage battery according to Comparative Examples 1 to 8 is obtained, and the results are shown in Table 1.
表１から、カルシウムのみを添加すると、正極板中に残存するカルシウムの量が少ない比較例２〜６に係る鉛蓄電池で、僅かに寿命サイクル比の向上が認められることがわかる。この比較例２〜６に係る鉛蓄電池は鉛粉に添加するカルシウムの量が０．１０質量％〜１．２０質量％であり、公知の条件での電槽化成に供する限りにおいては、カルシウムの添加量を上記した範囲にするのが好ましい。 From Table 1, it can be seen that when only calcium is added, the life cycle ratio is slightly improved in the lead storage batteries according to Comparative Examples 2 to 6 in which the amount of calcium remaining in the positive electrode plate is small. In the lead storage batteries according to Comparative Examples 2 to 6, the amount of calcium added to the lead powder is 0.10% by mass to 1.20% by mass, and as long as it is used for battery case formation under known conditions, The addition amount is preferably in the above range.
（評価試験２）
評価試験１の比較例１に対し、亜鉛を０．０１質量％、０．０５質量％、０．１０質量％、０．２０質量％、０．５０質量％、１．００質量％、２．００質量％、３．００質量％添加した実施例１、７、１３、１９、２５、３１、３７、４３；同比較例２〜６に対し、亜鉛を０．０１質量％、０．０５質量％、０．１０質量％、０．２０質量％、０．５０質量％、１．００質量％、２．００質量％、３．００質量％添加した実施例２、８、１４、２０、２６、３２、３８、４４；実施例３、９、１５、２１、２７、３３、３９、４５；実施例４、１０、１６、２２、２８、３４、４０、４６；実施例５、１１、１７、２３、２９、３５、４１、４７；実施例６、１２、１８、２４、３０、３６、４２、４８に係る鉛蓄電池を作製し、評価試験１と同様に正極板中に残存するカルシウムの量を測定し、結果を表２に示す。
(Evaluation test 2)
0.01% by weight, 0.05% by weight, 0.10% by weight, 0.20% by weight, 0.50% by weight, 1.00% by weight, and zinc for Comparative Example 1 in Evaluation Test 1. Examples 1, 7, 13, 19, 25, 31, 37, 43 added with 00% by mass and 3.00% by mass; 0.01% by mass and 0.05% by mass of zinc with respect to Comparative Examples 2 to 6 %, 0.10 mass%, 0.20 mass%, 0.50 mass%, 1.00 mass%, 2.00 mass%, 3.00 mass% added Example 2, 8, 14, 20, 26 , 32, 38, 44; Examples 3, 9, 15, 21, 27, 33, 39, 45; Examples 4, 10, 16, 22, 28, 34, 40, 46; Examples 5, 11, 17 , 23, 29, 35, 41, 47; producing lead acid batteries according to Examples 6, 12, 18, 24, 30, 36, 42, 48, and evaluation tests And measuring the amount of calcium remaining in the positive electrode plate in the same manner, the results are shown in Table 2.
表２から、亜鉛の添加量が０．０１質量％である実施例１〜６と、それが０．０５質量％である実施例７〜１２とは、カルシウムのみを添加した比較例１〜６と比較しても、正極板中に残存するカルシウムの量に変化は認められず、亜鉛の添加による効果が認められなかったが、カルシウムの添加量を０．１０質量％として亜鉛の添加量を０．１０質量％、０．２０質量％、０．５０質量％、１．００質量％、２．００質量％とした実施例１４、２０、２６、３２、３８；カルシウムの添加量を０．２０質量％として亜鉛の添加量を０．１０質量％、０．２０質量％、０．５０質量％、１．００質量％、２．００質量％とした実施例１５、２１、２７、３３、３９；カルシウムの添加量を０．５０質量％として亜鉛の添加量を０．１０質量％、０．２０質量％、０．５０質量％、１．００質量％、２．００質量％とした実施例１６、２２、２８、３４、４０；カルシウムの添加量を１．００質量％として亜鉛の添加量を０．１０質量％、０．２０質量％、０．５０質量％、１．００質量％、２．００質量％とした実施例１７、２３、２９、３５、４１；カルシウムの添加量を１．２０質量％として亜鉛の添加量を０．１０質量％、０．２０質量％、０．５０質量％、１．００質量％、２．００質量％とした実施例１８、２４、３０、３６、４２では、電解液中に溶出するカルシウムの量が抑制できて、正極板中に残存するカルシウムの量が増加できることがわかった。なお、亜鉛の添加量を３．００質量％とした実施例４３〜４８では、カルシウムの添加量が上記した０．１０〜１．２０質量％の場合であっても、亜鉛の添加量を２．００質量％とした実施例３８〜４２と比較して効果の差は認められないことがわかった。 From Table 2, Examples 1-6 whose addition amount of zinc is 0.01 mass% and Examples 7-12 whose it is 0.05 mass% are Comparative Examples 1-6 which added only calcium. Even when compared with the above, no change was observed in the amount of calcium remaining in the positive electrode plate, and no effect due to the addition of zinc was observed, but the addition amount of zinc was set to 0.10% by mass. Examples 14, 20, 26, 32, 38 with 0.10% by mass, 0.20% by mass, 0.50% by mass, 1.00% by mass, and 2.00% by mass; Examples 15, 21, 27, 33 in which the addition amount of zinc was 0.10% by mass, 0.20% by mass, 0.50% by mass, 1.00% by mass, and 2.00% by mass as 20% by mass, 39; Addition amount of calcium is 0.50 mass%, and addition amount of zinc is 0.10 mass% 0.20% by mass, 0.50% by mass, 1.00% by mass, 2.00% by mass Examples 16, 22, 28, 34, 40; Examples 17, 23, 29, 35, and 41 with addition amounts of 0.10 mass%, 0.20 mass%, 0.50 mass%, 1.00 mass%, and 2.00 mass%; addition amount of calcium The amount of zinc was 0.10% by mass, 0.20% by mass, 0.50% by mass, 1.00% by mass, and 2.00% by mass. 36 and 42, it was found that the amount of calcium eluted in the electrolyte solution could be suppressed and the amount of calcium remaining in the positive electrode plate could be increased. In Examples 43 to 48 in which the amount of zinc added was 3.00% by mass, the amount of zinc added was 2 even if the amount of calcium added was 0.10 to 1.20% by mass. It turned out that the difference of an effect is not recognized compared with Examples 38-42 set to 0.000 mass%.
（評価試験３）
評価試験２で、電解液中に溶出するカルシウムの量の抑制効果が大きかった実施例３２〜３６と評価試験１の比較例１に対する実施例３１とについて、評価試験１と同様に、充放電サイクル寿命試験に供し、従来例に係る鉛蓄電池の寿命時のサイクル数（寿命サイクル比）を１．００として、結果を表３に示す。
(Evaluation Test 3)
Similar to evaluation test 1, charge / discharge cycles were performed for evaluation examples 2 to 36 in which the effect of suppressing the amount of calcium eluted in the electrolytic solution was large and for example 31 to comparative example 1 of evaluation test 1. For the life test, the number of cycles (life cycle ratio) at the time of life of the lead-acid battery according to the conventional example is set to 1.00, and the results are shown in Table 3.
表３から、電解液中に溶出するカルシウムの量が抑制できた実施例３２〜３６では寿命サイクル比が向上できたことがわかる。なお、この評価試験３では、亜鉛の添加量を１．００質量％として、カルシウムの添加量を０．１０質量％、０．２０質量％、０．５０質量％、１．００質量％、１．２０質量％としたが、評価試験２で求めた、電解液中に溶出するカルシウムの量から判断して、亜鉛の添加量を０．１０〜２．００質量％として、カルシウムの添加量を０．１０質量％、０．２０質量％、０．５０質量％、１．００質量％、１．２０質量％としても、同様の効果が得られるものと推定される。 From Table 3, it can be seen that in Examples 32-36 in which the amount of calcium eluted in the electrolyte solution could be suppressed, the life cycle ratio could be improved. In this evaluation test 3, the amount of zinc added is 1.00% by mass, and the amount of calcium added is 0.10% by mass, 0.20% by mass, 0.50% by mass, 1.00% by mass, 20% by mass, but determined from the amount of calcium eluted in the electrolyte obtained in Evaluation Test 2, the amount of zinc added was 0.10 to 2.00% by mass, and the amount of calcium added was It is estimated that the same effect can be obtained even when the content is 0.10% by mass, 0.20% by mass, 0.50% by mass, 1.00% by mass, and 1.20% by mass.
（評価試験４）
評価試験３では、カルシウムの添加量が０．１０〜１．２０質量％で、亜鉛の添加量を１．００質量％とすることで良好な結果が得られることが確認できたが、これらの添加量を多くすることは正極活物質原料の質量％の減少につながるため、この評価試験４では、亜鉛の添加量が少なくてカルシウム添加の効果が得られるものとして、カルシウムの添加量を１．００質量％、亜鉛の添加量を０．２０質量％として、電解液中にカルシウムイオンまたはマグネシウムイオンを補うことで、効果を比較した。すなわち、電解液中にカルシウムイオンを０．０１ｇ／リットル、０．０５ｇ／リットル、０．１０ｇ／リットル、０．５０ｇ／リットル、１．００ｇ／リットル、５．００ｇ／リットル、１０．００ｇ／リットル、１５．００ｇ／リットル添加した実施例４９〜５６と、電解液中にマグネシウムイオンを０．０１ｇ／リットル、０．０５ｇ／リットル、０．１０ｇ／リットル、０．５０ｇ／リットル、１．００ｇ／リットル、５．００ｇ／リットル、１０．００ｇ／リットル、１５．００ｇ／リットル添加した実施例５７〜６４について、評価試験１と同様に正極板中に残存するカルシウムとマグネシウムの量を測定するとともに寿命サイクル比を求めて、結果を表４に示す。なお、カルシウムイオンまたはマグネシウムイオンは、硫酸カルシウムまたは硫酸マグネシウムを電解液中に添加することで補った。
(Evaluation Test 4)
In Evaluation Test 3, it was confirmed that good results were obtained when the addition amount of calcium was 0.10 to 1.20 mass% and the addition amount of zinc was 1.00 mass%. Since increasing the amount of addition leads to a decrease in the mass% of the positive electrode active material raw material, in this evaluation test 4, it is assumed that the effect of calcium addition can be obtained with a small amount of zinc added. The effect was compared by supplementing calcium ions or magnesium ions in the electrolytic solution with 00 mass% and zinc addition amount of 0.20 mass%. That is, 0.01 g / liter, 0.05 g / liter, 0.10 g / liter, 0.50 g / liter, 1.00 g / liter, 5.00 g / liter, 10.00 g / liter calcium ion in the electrolyte Examples 49 to 56 to which 15.00 g / liter was added, and magnesium ions in the electrolyte solution were 0.01 g / liter, 0.05 g / liter, 0.10 g / liter, 0.50 g / liter, 1.00 g / liter For Examples 57 to 64 to which liters, 5.00 g / liter, 10.00 g / liter, and 15.00 g / liter were added, the amounts of calcium and magnesium remaining in the positive electrode plate were measured in the same manner as in the evaluation test 1, and the lifetime was measured. The cycle ratio was determined and the results are shown in Table 4. In addition, calcium ion or magnesium ion was supplemented by adding calcium sulfate or magnesium sulfate to the electrolytic solution.
表４から、電解液中にカルシウムイオンまたはマグネシウムイオンを補うことによる効果が認められたのは０．１０〜１０．００ｇ／リットルであり、０．１０ｇ／リットル未満では効果は認められず、１０．００ｇ／リットルを超えると効果が飽和することがわかる。 From Table 4, the effect of supplementing calcium ions or magnesium ions in the electrolyte was recognized at 0.10 to 10.00 g / liter, and no effect was observed at less than 0.10 g / liter. It turns out that an effect is saturated when it exceeds 0.000 g / liter.
（評価試験５）
評価試験４で良好な結果が得られたカルシウムイオンまたはマグネシウムイオンの添加量が１０．００ｇ／リットルのもののうち、カルシウムイオンの添加量が１０．００ｇ／リットルのものについて、正極活物質原料中に添加するカルシウムの添加量を０．５０質量％として、亜鉛を０．２質量％とした実施例６５について、評価試験１と同様に正極板中に残存するカルシウムの量を測定するとともに寿命サイクル比を求めて、結果を表５に示す。
(Evaluation Test 5)
Of the calcium ion or magnesium ion addition amount of 10.00 g / liter for which good results were obtained in the evaluation test 4, those having a calcium ion addition amount of 10.00 g / liter are contained in the positive electrode active material raw material. About Example 65 which made the addition amount of calcium to add 0.50 mass% and made zinc 0.2 mass%, the amount of calcium remaining in the positive electrode plate was measured in the same manner as in the evaluation test 1, and the life cycle ratio The results are shown in Table 5.
表５から、カルシウムの添加量を０．５０質量％とした実施例６５は、それが１．００質量％である実施例６３とを比較すると、寿命サイクル比は低下するものの、従来例と比較して２倍以上であることから、カルシウムイオンの添加による効果があると考えられる。なお、マグネシウムイオンについても同様の効果があることが推定される。 From Table 5, although Example 65 which made the addition amount of calcium 0.50 mass% compares with Example 63 in which it is 1.00 mass%, it compares with a prior art example, although a life cycle ratio falls. Therefore, it is considered that there is an effect by adding calcium ions. In addition, it is estimated that a magnesium ion has the same effect.
（評価試験６）
評価試験４で良好な結果が得られたカルシウムイオンまたはマグネシウムイオンの添加量が１０．００ｇ／リットルのもののうち、カルシウムイオンの添加量が１０．００ｇ／リットルのものについて、正極活物質原料中に添加するカルシウムを１．００質量％として、亜鉛の添加量を２．０質量％とした実施例６６について、評価試験１と同様に正極板中に残存するカルシウムの量を測定するとともに寿命サイクル比を求めて、結果を表６に示す。
(Evaluation Test 6)
Of the calcium ion or magnesium ion addition amount of 10.00 g / liter for which good results were obtained in the evaluation test 4, those having a calcium ion addition amount of 10.00 g / liter are contained in the positive electrode active material raw material. For Example 66 in which the amount of calcium to be added was 1.00% by mass and the amount of zinc to be added was 2.0% by mass, the amount of calcium remaining in the positive electrode plate was measured in the same manner as in Evaluation Test 1, and the life cycle ratio was The results are shown in Table 6.
表６から、亜鉛の添加量を２．００質量％とした実施例６６は、それが０．２０質量％である実施例６３とを比較すると、寿命サイクル比はほとんど同じであることから、亜鉛の添加量が本発明の範囲内であれば、寿命には悪影響を及ぼさないことがわかる。 From Table 6, since Example 66 which made the addition amount of zinc 2.00 mass% compared with Example 63 in which it is 0.20 mass%, the life cycle ratio is almost the same. It can be seen that if the amount of the addition is within the range of the present invention, the lifetime is not adversely affected.
上記した評価試験では、カルシウムイオンまたはマグネシウムイオンを意図的に添加したものであるが、市販の鉛蓄電池では、正極活物質原料中に添加されたカルシウム又はその化合物が電槽化成時に溶出してカルシウムイオンとして存在しているが、本発明における数値は、このような溶出したカルシウムイオンも含むものである。 In the above-described evaluation test, calcium ions or magnesium ions are intentionally added. However, in a commercially available lead-acid battery, calcium added to the positive electrode active material material or its compound is eluted at the time of battery formation, and calcium is added. Although present as ions, the numerical values in the present invention include such eluted calcium ions.
上述した如く、本発明は、正極活物質原料中にカルシウム又はその化合物と亜鉛又はその化合物を含有させることで、カルシウムの溶出が防止でき、サイクル寿命特性の向上に寄与できるから、その産業上の利用可能性は大である。 As described above, the present invention can prevent calcium elution by containing calcium or a compound thereof and zinc or a compound thereof in the positive electrode active material raw material, and can contribute to improvement of cycle life characteristics. The availability is great.
Claims (3)
前記正極活物質原料は、０．１０質量％以上、１．２０質量％以下のカルシウムと、０．１０質量％以上、２．００質量％以下の亜鉛を含むことを特徴とする鉛蓄電池。 Using a positive electrode plate containing a positive electrode active material raw material containing lead as a main component, containing calcium or a compound thereof and zinc or a compound thereof,
The lead-acid battery characterized in that the positive electrode active material material contains 0.10 mass% or more and 1.20 mass% or less calcium and 0.10 mass% or more and 2.00 mass% or less zinc .
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