JPH01117273A - Lead-acid battery - Google Patents
Lead-acid batteryInfo
- Publication number
- JPH01117273A JPH01117273A JP62276952A JP27695287A JPH01117273A JP H01117273 A JPH01117273 A JP H01117273A JP 62276952 A JP62276952 A JP 62276952A JP 27695287 A JP27695287 A JP 27695287A JP H01117273 A JPH01117273 A JP H01117273A
- Authority
- JP
- Japan
- Prior art keywords
- discharge
- electrolyte
- alkaline
- metal ions
- exist
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 10
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims abstract description 6
- 229910017910 Sb—Zn Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910000978 Pb alloy Inorganic materials 0.000 claims abstract 2
- 239000000758 substrate Substances 0.000 claims description 7
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 1
- 230000002730 additional effect Effects 0.000 abstract 1
- 229910052745 lead Inorganic materials 0.000 abstract 1
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- 229910000882 Ca alloy Inorganic materials 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011149 active material Substances 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910001245 Sb alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052924 anglesite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
- H01M4/685—Lead alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明は鉛蓄電池の改良に関するものである。[Detailed description of the invention] Industrial applications The present invention relates to improvements in lead-acid batteries.
従来の技術
従来鉛蓄電池は、長期間放置されたり、過放電状態で放
置されたりすると、充電不可能な状態になり早期に寿命
となることが多い、そこで格子合金のＳｂを減らして自
己放電を減少させたり、Ｓｂを含まないＰｂ −Ｃａ合
金を使用して、自己放電を減少させている。また充電性
をよくするために電解液中にリン酸やアルカリイオンを
入れていた。Conventional technology If conventional lead-acid batteries are left unused for long periods of time or left in an over-discharged state, they often become unrechargeable and reach the end of their lifespan prematurely. Sb-free Pb--Ca alloys have been used to reduce self-discharge. Phosphoric acid and alkali ions were also added to the electrolyte to improve charging performance.
発明が解決しようとする問題点
ｐｂ −Ｓｂ系合金では、Ｓｂの水素過電圧が小さいた
め自己放電が大きく、更に充電時の水の分屏が多（水の
減少が大きいという欠点がある。−方、Ｐｂ −Ｃａ系
合金では、深い放電を行うサイクル使用において寿命が
著しく短く、更に長時間の連続放電や放電状態のまま開
路状態で放置した後の充電が困難になり、容量が極端に
減少する欠点などがある。またＣａｆｉ度が増加すると
格子集電体自身が粒界腐食によって伸びるという現象が
著しくなり、活物質保持が不能となったり、短絡の原因
となる。Problems to be Solved by the Invention In the pb-Sb alloy, self-discharge is large due to the small hydrogen overvoltage of Sb, and there is also a drawback that water is divided into large portions during charging (water loss is large). , Pb-Ca alloys have a significantly short lifespan when used in deep discharge cycles, and furthermore, it becomes difficult to charge them after long periods of continuous discharge or after being left in an open circuit state in a discharged state, resulting in an extremely reduced capacity. In addition, as the Cafi degree increases, the phenomenon that the lattice current collector itself stretches due to intergranular corrosion becomes significant, making it impossible to retain the active material or causing a short circuit.
一方、過放電されると電解液である硫酸濃度が著しく低
下して、電解液の伝導度が低くなるためやはり充電不能
となり、電解液の伝導性維持が問題の一つとなる。On the other hand, if the battery is over-discharged, the concentration of sulfuric acid, which is the electrolytic solution, decreases significantly and the conductivity of the electrolytic solution decreases, making it impossible to charge the battery, and maintaining the conductivity of the electrolytic solution becomes a problem.
問題点を解決するだめの手段
鉛蓄電池用格子基体の主たる役割は、活物質の保持と集
電機能にあり、機械的強度が高く、伝導性が良好である
という性質を維持するために耐食性も良好でなければな
らない。Ｓｂを含む合金は、活物質との密着性が良いと
いう長所があり、Ｓｂ濃変を、自己放電に影響を及ぼさ
ない範囲０．Ｏ１≦Ｓｂ≦０．１ｗｔ％に限定した。ま
たＣａは機械的強度の点で優れているので、サイクル容
量劣化と格子の伸びが少ない０．０９ｗｔ％未満に限定
した。さらにＺｎを含有させたＰｂ −Ｃａ −Ｓｂ
−Ｚｎ合金を使用することによって、自己放電が小さく
過放電特性および寿命特性を向上させることができる。The main role of the lattice substrate for lead-acid batteries is to hold the active material and collect current.In order to maintain the properties of high mechanical strength and good conductivity, the grid substrate for lead-acid batteries also has corrosion resistance. Must be in good condition. Alloys containing Sb have the advantage of good adhesion to the active material, and the change in Sb concentration can be kept within a range of 0.00000000 without affecting self-discharge. It was limited to O1≦Sb≦0.1wt%. Further, since Ca is excellent in terms of mechanical strength, it is limited to less than 0.09 wt%, which causes less deterioration of cycle capacity and less elongation of the lattice. Pb-Ca-Sb further containing Zn
- By using the Zn alloy, self-discharge is small and over-discharge characteristics and life characteristics can be improved.
一方、電解液にはアルカリ金属イオンまたはアルカリ土
類金属イオン（アルカリ土類金属の水和物イオンを含む
）が存在し、合金の効果と存在イオンの効果の増成また
は相乗性により、自己放電や過放電放置特性を実用上十
分に満足し得るものとなる。On the other hand, the electrolyte contains alkali metal ions or alkaline earth metal ions (including alkaline earth metal hydrate ions), and self-discharge occurs due to the effect of the alloy and the synergistic effect of the existing ions. The over-discharge characteristics and over-discharge characteristics are sufficiently satisfactory for practical purposes.
作用
自己放電性能、長期保存性能、過放電放置特性の向上が
図れる。It is possible to improve self-discharge performance, long-term storage performance, and over-discharge storage characteristics.
実施例
Ｐｂ −Ｃａ −Ｓｂ系合金にＺｎを添加することによ
って過充電特性、サイクル寿命、保存性能および過放゛
電特性に効果がある。これはＺｎとＳｂとの間で５ｂｔ
Ｚｎｓ及び５ｂｓＺｎａなる化合物が生成して保存性能
や耐食性に関しても従来の合金に比較して、非常に優れ
たものとなる。Example Adding Zn to the Pb-Ca-Sb alloy has effects on overcharge characteristics, cycle life, storage performance, and overdischarge characteristics. This is 5bt between Zn and Sb.
Compounds Zns and 5bsZna are produced, and the storage performance and corrosion resistance are also very superior compared to conventional alloys.
一方、電解液中の添加物については、過放電後Ｈす・→
Ｈ，０１Ｓ０４ト→ＰｂＳＯ４となるため、充電電流の
担い手としてＳＯ４”−塩のカチオンが必要である。な
かでも電池の他の性質（寿命、容量）への影響を考慮し
て選択しなければならない、その中でアルカリ金属イオ
ンまたはアルカリ土類金属イオン（水和物イオンも含む
）が伝導度として良好であったため、これを選択した。On the other hand, regarding additives in the electrolyte, H after overdischarge →
Since H,01S04 becomes PbSO4, an SO4”-salt cation is required as a carrier of the charging current.The selection must be made taking into consideration the effect on other properties of the battery (life, capacity). Among them, alkali metal ions or alkaline earth metal ions (including hydrate ions) were selected because they had good conductivity.
本発明の一実施例について説明する。An embodiment of the present invention will be described.
純ｐｂに０．０６ｗｔ％のＣａ、、０．０５ｗｔ％のＳ
ｂおよび０．５−ｔ％のＺｎを含む格子基体を作製し、
ペーストを充填して通常の熟成、乾燥を行って正極板と
した。化成を行った後蓄電池を組み立て４Ａｈ−４Ｖの
電池を製造した。なお比較例としてＰｂ−ＣａＯ０１％
合金でも同様の実験を行った。0.06wt% Ca, 0.05wt% S in pure PB
A lattice substrate containing b and 0.5-t% Zn was prepared,
A positive electrode plate was obtained by filling the paste with conventional aging and drying. After chemical formation, a storage battery was assembled to produce a 4Ah-4V battery. As a comparative example, Pb-CaO01%
Similar experiments were conducted with alloys.
電解液にはＮａｔＳＯ！’Ｆ’Ｙ；’ｓＯａ ” ７
ＨｚＯをそれぞれ所定濃度（０，１＋＋＋ｏｌ／ｌ）に
調整し、単独あるいはその混合溶液を電池に注液した。NatSO for electrolyte! 'F'Y;'sOa'' 7
HzO was adjusted to a predetermined concentration (0, 1 +++ ol/l), and a single solution or a mixed solution thereof was injected into the battery.
このようにして作製した鉛蓄電池を用いて次の特性を評
価した。The following characteristics were evaluated using the lead-acid battery thus produced.
１ 容量回復率
当該電池を充電後１．７Ωで２４時間放電し、１Ａ月間
２５°Ｃ中で放置して放置後４．９ Ｖ （１，２Ａ制
限）の定電圧充電を２４時間行って初期容量との割合を
算出した。1 Capacity recovery rate After charging the battery, discharge it at 1.7 Ω for 24 hours, leave it at 25°C for 1 A month, and then charge it at a constant voltage of 4.9 V (limited to 1,2 A) for 24 hours to recover the initial value. The ratio with the capacity was calculated.
２ 過充電特性
当該電池を２５℃において１．２Ａで７日間充電した後
同様な充放電をくり返し放電容量が初期の６０％になる
までの充電電気量で過充電特性を評価した。2. Overcharge characteristics After charging the battery at 1.2 A at 25° C. for 7 days, the same charging and discharging process was repeated, and overcharge characteristics were evaluated based on the amount of electricity charged until the discharge capacity reached 60% of the initial value.
３ サイクル寿命
放電電流８００ｍＡで３．４ｖまで放電し、４００ｍＡ
で１１時間充電をする充放電サイクルを繰り返し放電時
間が初期の６０％になるまでのサイクル数を測定した。3 Cycle life Discharge to 3.4V at a discharge current of 800mA, 400mA
A charge/discharge cycle of charging for 11 hours was repeated, and the number of cycles until the discharge time reached 60% of the initial value was measured.
４ 保存性能
当該電池を充電後４５°Ｃ気相中に放置して３Ａ月後の
容量を測定し、初期容量に対する割合を算出した。4. Storage performance After charging, the battery was left in a gas phase at 45°C, and the capacity was measured after 3 A months, and the ratio to the initial capacity was calculated.
以上の試験で得られた結果を第１表に示す。The results obtained in the above tests are shown in Table 1.
第１表は、Ｐｂ −Ｃａ −Ｓｂ −Ｚｎ合金格子とＰ
ｂ −Ｃａ合金格子における電池性能を、更に電解液中
の添加剤の有無あるいは違いを含めて検討した結果を示
したものである。Table 1 shows the Pb-Ca-Sb-Zn alloy lattice and Pb-Ca-Sb-Zn alloy lattice.
This figure shows the results of examining the battery performance in the b-Ca alloy lattice, including the presence or absence of additives in the electrolytic solution.
第１表かられかるようにＰｂ −Ｃａ合金と比較し・て
過充電特性、保存性能、過放電放置性能及びサイクル寿
命は、いずれも優れていることがわかる。また電解液添
加剤について無添加よりもＨａ富ＳＯａ、ＭｇＳＯ４、
Ｍｇ５Ｏａ ” ７ＨｍＯをそれぞれ添加した方が、
すべての性能でより良好な結果を示し、特に過放電放置
性能においては、無添加より遥かに優れており、Ｐｂ
−Ｃａ −Ｓｂ −Ｚｎ合金格子基体のみの効果と添加
剤の効果とが共存することで加酸または相乗することが
わかった。また図面からＣａ濃度が０．０９ｗｔ％以上
になると伸びが急激に増加する。従って、Ｃａ濃度は、
格子基体の伸びが少ない０．０９ｗｔ％未満に限定した
。As can be seen from Table 1, it is found that the overcharge characteristics, storage performance, overdischarge storage performance, and cycle life are all superior compared to the Pb--Ca alloy. Regarding electrolyte additives, Ha-rich SOa, MgSO4,
It is better to add Mg5Oa ”7HmO respectively,
It showed better results in all performances, and in particular, in overdischarge storage performance, it was far superior to no additives, and Pb
It was found that the effect of the -Ca-Sb-Zn alloy lattice substrate alone and the effect of the additive coexist, resulting in oxidation or synergistic effect. Moreover, from the drawing, when the Ca concentration becomes 0.09 wt% or more, the elongation increases rapidly. Therefore, the Ca concentration is
The amount was limited to less than 0.09 wt%, which causes less elongation of the lattice substrate.
発明の効果
びサイクル寿命において改善でき、また電解液にアルカ
リ金属イオン、アルカリ土類金属イオンを添加すること
により、加酸または相乗的に効果がある等工業的価値甚
だ大なるものである。The effects and cycle life of the invention can be improved, and addition of alkali metal ions and alkaline earth metal ions to the electrolytic solution has an acidic or synergistic effect, which has great industrial value.
図面はＰｂ −Ｃａ系合金中のＣａ濃度に対する格子基
体の伸び比を示す曲線図である。The drawing is a curve diagram showing the elongation ratio of the lattice substrate to the Ca concentration in the Pb-Ca alloy.
Claims (1)
％のＳｂからなる鉛合金にＺｎを添加したＰｂ−Ｃａ−
Ｓｂ−Ｚｎ合金からなる極板基体を用い電解液中にアル
カリ金属イオンまたはアルカリ土類金属イオンが存在す
ることを特徴とする鉛蓄電池。Less than 0.09wt% Ca and 0.01-0.1wt
Pb-Ca- with Zn added to a lead alloy consisting of % Sb
1. A lead-acid battery characterized in that an electrode plate substrate made of an Sb-Zn alloy is used and alkali metal ions or alkaline earth metal ions are present in the electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62276952A JPH01117273A (en) | 1987-10-30 | 1987-10-30 | Lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62276952A JPH01117273A (en) | 1987-10-30 | 1987-10-30 | Lead-acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01117273A true JPH01117273A (en) | 1989-05-10 |
Family
ID=17576700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62276952A Pending JPH01117273A (en) | 1987-10-30 | 1987-10-30 | Lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01117273A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009152132A (en) * | 2007-12-21 | 2009-07-09 | Gs Yuasa Corporation | Lead-acid storage battery |
-
1987
- 1987-10-30 JP JP62276952A patent/JPH01117273A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009152132A (en) * | 2007-12-21 | 2009-07-09 | Gs Yuasa Corporation | Lead-acid storage battery |
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