JPH01267965A - Sealed lead-acid battery - Google Patents
Sealed lead-acid batteryInfo
- Publication number
- JPH01267965A JPH01267965A JP63096364A JP9636488A JPH01267965A JP H01267965 A JPH01267965 A JP H01267965A JP 63096364 A JP63096364 A JP 63096364A JP 9636488 A JP9636488 A JP 9636488A JP H01267965 A JPH01267965 A JP H01267965A
- Authority
- JP
- Japan
- Prior art keywords
- concentration
- quaternary ammonium
- ammonium ions
- ion
- electrolyte
- 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 6
- -1 ammonium ions Chemical class 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 229910000838 Al alloy Inorganic materials 0.000 claims 1
- 229910001128 Sn alloy Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 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 abstract 2
- 229910052924 anglesite Inorganic materials 0.000 abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 6
- 235000011130 ammonium sulphate Nutrition 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 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
- 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
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明は密閉形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 sealed lead-acid batteries.
従来の技術とその課題
密閉形鉛蓄電池は電解液が外部に漏れないのでポータプ
ル電子機器の小型電源として広く普及している。近年密
閉形鉛蓄電池は小形軽量化や高性能化が進み、限られた
スペース内により多くの活物質を入れる必要に迫られて
、１セル当たりの活物質量に対する硫酸量の割合が小さ
くなってきている。したがって過放電または長期放置に
よる自己放電などの原因により電解液比重の著しい低下
を生じる。を解液中の硫酸濃度（比重）が低下すると、
極板中に生成した硫酸鉛は次の表に見るごとく、硫酸濃
度の低下と共に溶解度が大きくなり、特に硫酸が著しく
少ない領域では激増する。Conventional technology and its problems Sealed lead-acid batteries are widely used as small power sources for portable electronic devices because their electrolyte does not leak outside. In recent years, sealed lead-acid batteries have become smaller and lighter and have higher performance, and as a result, it is necessary to fit more active material into a limited space, and the ratio of sulfuric acid to the amount of active material per cell has become smaller. ing. Therefore, due to causes such as overdischarge or self-discharge due to long-term storage, the electrolyte specific gravity significantly decreases. When the sulfuric acid concentration (specific gravity) in the solution decreases,
As shown in the table below, the solubility of lead sulfate formed in the electrode plate increases as the sulfuric acid concentration decreases, and it increases dramatically especially in areas where sulfuric acid is extremely low.
その後の周囲温度の変化や充電などのために硫酸鉛の比
較的大きな結晶や鉛の針状結晶が極板表面に析出する。Due to subsequent changes in ambient temperature and charging, relatively large crystals of lead sulfate and needle-shaped lead crystals are deposited on the surface of the electrode plate.
このように充電しても元に戻り難い結晶性硫酸鉛が生成
すると、再充電が困難になリ、電池容量や放電電圧が低
下しなり、また鉛の針状結晶生成はセパレータを貫通し
て内部短絡の原因となっていた。The formation of crystalline lead sulfate, which is difficult to return to its original state even after charging, makes recharging difficult and reduces battery capacity and discharge voltage.Also, the formation of needle-shaped lead crystals can penetrate the separator. This caused an internal short circuit.
これらの欠点を解消する目的で硫酸ナトリウムや硫酸カ
リウムなどのアルカリ金属の硫酸塩や硫酸アンモニウム
などの添加による改良が試みられているが、アルカリ金
属の場合は、添加量が少ないと効果に乏しく、また多量
に添加すると蓄電池の内部抵抗の増加、活物質細孔内へ
の電解液の浸透力の低下、電解液中の水素イオン濃度の
減少などにより容量や放電電圧の低下をもたらす欠点が
あった。また硫酸アンモニウムの添加はアンモニウムイ
オン（ＮＨ４＋）が酸化を受けやすく、酸化によりＮｏ
２−やＮ０ｓ−を生じ、格子の腐食やシャトル作用によ
り自己放電を促進したり、さらに硫酸アンモニウムは弱
塩基性塩のため電離度が小さくｎ２”の生成を抑制する
効果に乏しいものであった。In order to eliminate these drawbacks, improvements have been attempted by adding alkali metal sulfates such as sodium sulfate and potassium sulfate, and ammonium sulfate, but in the case of alkali metals, they are ineffective if added in small amounts, When added in large amounts, there are drawbacks such as an increase in the internal resistance of the storage battery, a decrease in the permeability of the electrolyte into the pores of the active material, and a decrease in the concentration of hydrogen ions in the electrolyte, resulting in a decrease in capacity and discharge voltage. In addition, when ammonium sulfate is added, ammonium ions (NH4+) are easily oxidized, and due to oxidation, No.
2- and N0s- are generated, which promotes self-discharge due to lattice corrosion and shuttle action. Furthermore, since ammonium sulfate is a weakly basic salt, its degree of ionization is small and it is not effective in suppressing the generation of n2''.
課題を解決するための手段
本発明は電解液に対し溶解度が大きく、かつ電離度が著
しく大きい第４アンモニウムイオンを添加することによ
り上記欠点を解消した密閉形鉛蓄電池を提供するもので
、水酸化第４アンモニウムイオンは電子構造から見て水
酸化ナトリウムや水酸化カリウムに相当する塩基性をも
っている。Means for Solving the Problems The present invention provides a sealed lead-acid battery that eliminates the above drawbacks by adding quaternary ammonium ions that have a high solubility in the electrolytic solution and a significantly high degree of ionization. The quaternary ammonium ion has basicity corresponding to sodium hydroxide or potassium hydroxide in terms of its electronic structure.
作用
この第４アンモニウムイオンを電解液に添加することに
よる作用は分析化学で共通イオン効果と呼ばれているも
ので、その原理を電解液中のＰｂ２＋の濃度について略
述する。Effect The effect of adding quaternary ammonium ions to the electrolytic solution is called the common ion effect in analytical chemistry, and its principle will be briefly explained with regard to the concentration of Pb2+ in the electrolytic solution.
いま、ｐｂ ｓ Ｏ４１モルが単独に溶液中にあると、
その電離度をα′とすれば、門ＳＱ、、Ｐｂ２”。Now, if 1 mole of pb s O4 is alone in solution,
If the degree of ionization is α', the gate SQ,,Pb2''.
３０４ ’−のそれぞれはつぎのように分配する。304'- are distributed as follows.
Ｐｂ５Ｏａ ｄＰｂ２”＋ｓＯｉ ２−１−α′ α′
α′
この反応の平衡定数Ｋｐｂは［Ｐｔ２”］ ［ＳＯ０
’−］／ ［Ｐｔ） Ｓ Ｏａコ＝α’２／（１−α′
）で表わされ、α′の大きさは１ｘｌＯ−’ ｇ／ｌ
程度で、したがってｐｂｓｏ、はほとんど１と見なすこ
とができる。Pb5Oa dPb2"+sOi 2-1-α'α'
α′ The equilibrium constant Kpb of this reaction is [Pt2”] [SO0
'-]/ [Pt) S Oa = α'2/(1-α'
), and the size of α' is 1xlO-' g/l
degree, and therefore pbso, can be considered almost 1.
第４アンモニウム（ここでは記号Ａで表わす）の硫酸塩
１モルが単独に溶液１ｊ２中にあるときの７４８度をβ
′とすると
ＡＳＯ，ａｌ“＋３０４ ’−
１−β′ β′ β′
硫酸第４アンモニウムは強電解質なので、電離度β′は
大きくほぼ１と見なすことができる。When 1 mole of quaternary ammonium sulfate (denoted here by the symbol A) is alone in solution 1j2, 748 degrees is β
', then ASO, al"+304 '- 1-β'β'β' Since quaternary ammonium sulfate is a strong electrolyte, the degree of ionization β' can be considered to be large and approximately 1.
次に硫酸鉛と硫酸第４アンモニウムが同一溶液に混在し
ている場合を考えると、それらのｖｈＭ度をそれぞれα
、βとすれば各成分の配分は次のようになる。Next, considering the case where lead sulfate and quaternary ammonium sulfate are mixed in the same solution, their vhM degrees are α
, β, the distribution of each component is as follows.
Ｐｂ５Ｏ＜！ＰｂＰｂＳＯ４２−
１−α α α
ＡＳＯ，！Ａ２”＋３０．２−
１−β β β
第４アンモニウムイオンは他のどんなイオンの影響も受
けないので充分型Ｍすると考えられ、β′中βと見なす
ことができる。Pb5O<! PbPbSO42- 1-α α α ASO,! A2''+30.2- 1-β β β Since the quaternary ammonium ion is not affected by any other ions, it is considered to be sufficiently type M, and can be regarded as β in β'.
［Ｐｂ２”］＝α、［３０４’−］＝α＋β。[Pb2'']=α, [304'-]=α+β.
Ｐｂ５Ｏａ＝１−α
Ｋｐｂ＝α’２／＜１−α′ ）
＝α（α±β）／（１−α）
１−α′＝１−α＝β中１なので、
α′２；α２＋α、したがってα′〉αすなわち弱電解
質のｐｂｓｏ、は５ｏ４２−という共通イオンを持つ第
４アンモニウムが共存するとその電離度が小さくなり、
肺２４の濃度は小さく抑えられる。Pb5Oa=1-α Kpb=α'2/<1-α') = α(α±β)/(1-α) 1-α'=1-α=1 in β, so α'2; α2+α, Therefore, the degree of ionization of α'〉α, that is, the weak electrolyte pbso, decreases when quaternary ammonium having a common ion of 5o42- coexists.
The concentration in the lungs 24 is kept small.
ｐｂｓｏ、と第４アンモニウム塩の濃度をそれぞれＣｐ
ｂ、Ｃｔａとすれば、
ｐｂ？の濃度［Ｐｂ２＋］＝αｃｐｂ、 Ｓｏ、 ２−
イオン濃度［Ｓ Ｏａ ’ ］ ＝ ａ Ｃｐｂ＋βＣ
ｊａ、 Ｐｂ Ｓ Ｏ４濃度［ＰｂＳＯ４］ ＝ （１
−α）ＣｐｂＫｐｂ＝ ［Ｐｂ”］ ［ＳＯ０”］
／ ［Ｐｂ２＋］＝αｃｐｂ（ａＣｐｂ＋βＣｔａ）
／ （１−ａ ） Ｃａｂｌ−α中１．βキ１と考えら
れるから、Ｋρｂ−ａ２Ｃｐｂ＋αＣｔａ
極端な場合としてＣｐｂ＝ Ｃｔａ＝ Ｃとすれば、Ｋ
ｐｂ＝α（α＋１）Ｃ
α＋１中１とすれば、α＝ Ｋ ｐｂ／ ＣすなわちＰ
ｂ Ｓ Ｏ４の電離度（Ｐｂ ２”の濃度）は添加する
第４アンモニウムイオンの濃度に反比例することがわか
る。pbso, and quaternary ammonium salt concentration as Cp, respectively.
If b and Cta, then pb? Concentration of [Pb2+] = αcpb, So, 2-
Ion concentration [SOa'] = a Cpb+βC
ja, Pb SO4 concentration [PbSO4] = (1
−α) CpbKpb= [Pb”] [SO0”]
/ [Pb2+]=αcpb(aCpb+βCta)
/ (1-a) 1 in Cabl-α. Since βki1 is considered, Kρb-a2Cpb+αCta In the extreme case, if Cpb=Cta=C, then K
pb=α(α+1)C If 1 in α+1, then α=K pb/C, that is, P
It can be seen that the degree of ionization of bS O4 (concentration of Pb 2'') is inversely proportional to the concentration of quaternary ammonium ions added.
実施例
本発明ははじめに記した鉛電池の欠点を改良するもので
あり、以下本発明に至った実験の結果を説明する。EXAMPLE The present invention improves the drawbacks of lead batteries described at the beginning, and the results of experiments that led to the present invention will be explained below.
第１表に示すごとく電解液に各種添加物を加え５Ａｈの
電池を供試し、次の実験を行った。Various additives were added to the electrolytic solution as shown in Table 1, and a 5Ah battery was used for the following experiment.
実験１
２０ ＨＲ電流にて端子間電圧がＯｖになるまで放電し
、引き続き端子間を短絡して１５０時間放！放置そのの
ち２．２５Ｖ／セルの定電圧で充電を行い、その３０分
目の電流と５時間目充電電流値を調べる。Experiment 1 Discharge with 20 HR current until the voltage between the terminals reaches Ov, then short-circuit the terminals and leave it for 150 hours! After leaving it for a while, it was charged at a constant voltage of 2.25 V/cell, and the current at 30 minutes and the charging current value at 5 hours were checked.
実験２
定電流で完全に充電した後、２０ＨＲ電流にて端子間電
圧がＯｖになるまで放！し、引き続き端子間を短絡して
４０℃にて６ケ月問および１２ケ月間の保存を行い、１
０１１Ｒ電流にて定格容量の２００％の充電を行い容量
の回復率を調べる。結果を第１表に示す。Experiment 2 After fully charging with constant current, discharge with 20HR current until the voltage between the terminals reaches Ov! Then, short-circuit the terminals and store at 40℃ for 6 months and 12 months.
Charge to 200% of the rated capacity with 011R current and examine the capacity recovery rate. The results are shown in Table 1.
実験１の結果から、実験方法に示すごとき放置条件及び
充電条件では、第４アンモンニウムイオンであるテトラ
メチルアンモニウムイオンやテトラエチルアンモニウム
イオンを電解液に添加すれば充電受は入れは従来のもの
に比べ改善され、しかも添加量が少なくても同様の作用
を有することがわかる。実験２の結果から、実験方法に
示すように長期放置条件及び充電条件においては第４ア
ンモニウムイオンの存在が有効であることがわかる。ま
た、これらを添加したセルはいずれも放置後の充電で内
部短絡を生じるものは見られなかった。From the results of Experiment 1, under the standing and charging conditions shown in the experimental method, if quaternary ammonium ions such as tetramethylammonium ion and tetraethylammonium ion are added to the electrolyte, the charging capacity will be improved compared to the conventional one. It can be seen that the effect is improved and the same effect can be obtained even if the amount added is small. The results of Experiment 2 show that the presence of quaternary ammonium ions is effective under long-term storage conditions and charging conditions as shown in the experimental method. In addition, no internal short circuit was observed in any of the cells to which these were added during charging after being left unused.
また、本発明は第４アンモニウム塩単独の添加に限らず
燐酸や硼酸などを併用することは何等差支えない。Furthermore, the present invention is not limited to the addition of a quaternary ammonium salt alone, and may be used in combination with phosphoric acid, boric acid, etc.
発明の効果
テトラメチルアンモニウムイオンあるいはテトラエチル
アンモニウムイオンを電解液に添加することにより電解
液の低比重領域でのＰｂ ２”の溶解量を低く抑えて、
結晶成長を妨げ、しかも第４アンモニウムイオンの存在
により、電解液の電導度を大きく低下させることがない
ため回復充電特性が改良されると共に、セパレータ貫通
ショートもなくなり、過放電や長期放置に耐える電池を
提供することができ、その工業的価値は大である。Effects of the invention By adding tetramethylammonium ions or tetraethylammonium ions to the electrolytic solution, the amount of Pb 2'' dissolved in the low specific gravity region of the electrolytic solution can be suppressed to a low level.
The presence of quaternary ammonium ions prevents crystal growth and does not significantly reduce the conductivity of the electrolyte, improving recovery charging characteristics, eliminating short-circuits through the separator, and making the battery resistant to overdischarge and long-term storage. It is of great industrial value.
Claims (1)
−アルミニウム合金を正極格子に用いると共に、電解液
に第４アンモニウムイオンを含む密閉形鉛蓄電池。1. A sealed lead-acid battery using a lead-calcium-tin alloy or a lead-calcium-tin-aluminum alloy for the positive electrode grid and containing quaternary ammonium ions in the electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63096364A JPH01267965A (en) | 1988-04-19 | 1988-04-19 | Sealed lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63096364A JPH01267965A (en) | 1988-04-19 | 1988-04-19 | Sealed lead-acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01267965A true JPH01267965A (en) | 1989-10-25 |
Family
ID=14162929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63096364A Pending JPH01267965A (en) | 1988-04-19 | 1988-04-19 | Sealed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01267965A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008152973A (en) * | 2006-12-14 | 2008-07-03 | Osaka Univ | Electrolytic solution for lead storage battery, anode for lead storage battery, lead storage battery equipped with electrolytic solution and/or anode, and additive for lead acid battery |
| US9356321B2 (en) | 2012-12-21 | 2016-05-31 | Panasonic Intellectual Property Management Co., Ltd. | Lead-acid battery |
| WO2019088040A1 (en) | 2017-10-31 | 2019-05-09 | 日本板硝子株式会社 | Lead storage battery separator and lead storage battery |
-
1988
- 1988-04-19 JP JP63096364A patent/JPH01267965A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008152973A (en) * | 2006-12-14 | 2008-07-03 | Osaka Univ | Electrolytic solution for lead storage battery, anode for lead storage battery, lead storage battery equipped with electrolytic solution and/or anode, and additive for lead acid battery |
| US9356321B2 (en) | 2012-12-21 | 2016-05-31 | Panasonic Intellectual Property Management Co., Ltd. | Lead-acid battery |
| WO2019088040A1 (en) | 2017-10-31 | 2019-05-09 | 日本板硝子株式会社 | Lead storage battery separator and lead storage battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2008130516A (en) | Liquid lead-acid storage battery | |
| JP2002260714A (en) | Valve controlled lead storage battery | |
| JPS63213264A (en) | Lead storage battery | |
| JPH01267965A (en) | Sealed lead-acid battery | |
| JP2007035339A (en) | Control valve type lead-acid storage battery | |
| JPS58117658A (en) | Sealed lead-acid battery | |
| JP3216450B2 (en) | Electrolyte for lead-acid batteries | |
| US3447971A (en) | Neutral secondary battery | |
| JPH04179063A (en) | Sealed type lead-acid battery | |
| KR950004457B1 (en) | Lead battery | |
| JP2553858B2 (en) | Lead acid battery | |
| JP2959108B2 (en) | Lead storage battery | |
| JP3094423B2 (en) | Lead storage battery | |
| JPS63244568A (en) | Lead-acid battery | |
| JPH01117279A (en) | Lead-acid battery | |
| JPS6319771A (en) | Function recovery agent of lead-acid battery and its function recovery method | |
| JP3582068B2 (en) | How to charge lead storage batteries | |
| JP2808685B2 (en) | Lead storage battery | |
| JP2762730B2 (en) | Nickel-cadmium storage battery | |
| JPS6327827B2 (en) | ||
| JPS5819876A (en) | Electrolyte | |
| JPS61198574A (en) | Lead storage battery | |
| JPS5929375A (en) | Sealed lead storage battery | |
| JPS58197664A (en) | Alkaline zinc secondary battery | |
| JPS63211574A (en) | Sealed lead-acid battery |