JPH03276561A - Sealed lead-acid battery - Google Patents
Sealed lead-acid batteryInfo
- Publication number
- JPH03276561A JPH03276561A JP2077355A JP7735590A JPH03276561A JP H03276561 A JPH03276561 A JP H03276561A JP 2077355 A JP2077355 A JP 2077355A JP 7735590 A JP7735590 A JP 7735590A JP H03276561 A JPH03276561 A JP H03276561A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- antimony
- active material
- added
- discharge capacity
- 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.)
- Granted
Links
- 239000002253 acid Substances 0.000 title description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 32
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007774 positive electrode material Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 10
- 150000001463 antimony compounds Chemical class 0.000 claims abstract description 6
- 229910000978 Pb alloy Inorganic materials 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 16
- 239000011149 active material Substances 0.000 abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 230000006866 deterioration Effects 0.000 abstract description 6
- 230000003111 delayed effect Effects 0.000 abstract description 2
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 abstract 3
- 241001676573 Minium Species 0.000 abstract 2
- 230000000694 effects Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は密閉式鉛蓄電池の改良に関するもので、特に放
電容量およびサイクル寿命性能の優れた密閉式鉛蓄電池
を提供することを目的とするものである。[Detailed Description of the Invention] Industrial Application Field The present invention relates to improvements in sealed lead-acid batteries, and particularly aims to provide a sealed lead-acid battery with excellent discharge capacity and cycle life performance. .
従来の技術とその課題
現在、密閉式鉛蓄電池としては、格子合金にｈ−〇系合
金を用い、電解液は（１）微細ガラス繊維セパレータに
電解液を含浸させたリテーナ式と、（２）電解液にコロ
イダルシリカを添加してゲル状にしたゲル式の二種類が
あるが、従来の開放形液式電池に比べると前者は電解液
量が少ないため、また後者はＨ１−ＳＯ，の拡散が著し
く遅いために、放電容量が２０〜３０％も少なく、しか
もいずれも充放電中の極板内部の電解液比重の変化が著
しく大きいため、充放電サイクルが進むにつれ活物質の
劣化、特に活物質粒子の結合力の低下による正極板性能
の低下が生じている。Conventional technology and its issues Currently, sealed lead-acid batteries use h-0 series alloy as the lattice alloy and use the electrolyte as (1) a retainer type in which a fine glass fiber separator is impregnated with the electrolyte; (2) There are two types of gel-type batteries in which colloidal silica is added to the electrolyte to make it gel-like. Compared to conventional open-type batteries, the former uses a smaller amount of electrolyte, and the latter requires less diffusion of H1-SO. Because of this extremely slow discharge capacity, the discharge capacity is 20 to 30% lower, and in both cases, the change in the specific gravity of the electrolyte inside the electrode plates during charging and discharging is extremely large, so as the charge/discharge cycle progresses, the active material deteriorates, especially the active material. The performance of the positive electrode plate is decreasing due to a decrease in the bonding force of material particles.
正極活物質原料には主としてＰｂＯが、そして５％程度
のｐｂ、 ｏ、が使用されている。従来からｐｂ、 ｏ
、は添加量を増大させるにつれて、化成効率が向上し、
放電容量を増加させることができることはよく知られて
いる。しかし添加量を多くすると、原因はよくわからな
いが、上記正極活物質の劣化が起こり、寿命性能が悪く
なる。PbO is mainly used as the raw material for the positive electrode active material, and about 5% of PB, O, is used. Traditionally pb, o
, the chemical conversion efficiency improves as the amount added increases,
It is well known that discharge capacity can be increased. However, if the amount added is increased, the above-mentioned positive electrode active material deteriorates, although the cause is not well understood, and the life performance deteriorates.
また、正極活物質の劣化を防ぐために正極格子にｐｂ−
ｓｂ金合金用いる方法が提案されている（特公平１−９
３０５８号）が、格子合金中のアンチモン量を多くする
と、充放電サイクル中に正極格子から溶出したアンチモ
ンが負極板に析出して、負極板の性能を低下させるため
に、実際には上記方法を使用することは出来なかった。In addition, in order to prevent deterioration of the positive electrode active material, pb-
A method using sb gold alloy has been proposed (Japanese Patent Publication No. 1-9
No. 3058), when the amount of antimony in the lattice alloy is increased, the antimony eluted from the positive electrode lattice during charge/discharge cycles will precipitate on the negative electrode plate, degrading the performance of the negative electrode plate. It was not possible to use it.
課題を解決するための手段
本発明は密閉式鉛蓄電池において放電容量およびサイク
ル寿命性能を向上させることを目的とするもので、その
要旨は実質的にアンチモンを含まない鉛合金からなる正
極格子を使用し、正極活物質中に１５％以上の鉛丹（Ｐ
ｂ、 Ｏ，）および０．０５〜１．０ｗｔ％のアンチモ
ンあるいはアンチモン化合物の粉末を添加することに特
徴があり、さらに電解液に正極活物質１ｇ当り１〜５０
■９のリン酸を添加することが好ましい。Means for Solving the Problems The present invention aims to improve the discharge capacity and cycle life performance of sealed lead-acid batteries, the gist of which is to use a positive electrode grid made of a lead alloy substantially free of antimony. However, the positive electrode active material contains 15% or more of lead red (P).
b, O,) and 0.05 to 1.0 wt% of antimony or antimony compound powder, and further contains 1 to 50 wt% of antimony or antimony compound powder per 1 g of positive electrode active material to the electrolyte.
(2) It is preferable to add phosphoric acid in step 9.
作用
正極活物質中にｐｂ ｓ Ｏａを多く添加すると放電容
量は増加するが、寿命性能は低下する。しかし、活物質
中にアンチモン粉末を添加すれば正極活物質粒子間の結
合力が増加して正極板の劣化を遅らせることができる。When a large amount of PB s Oa is added to the working cathode active material, the discharge capacity increases, but the lifetime performance decreases. However, if antimony powder is added to the active material, the bonding force between the particles of the positive electrode active material increases, and the deterioration of the positive electrode plate can be delayed.
さらに電解液にリン酸を入れると活物質にαｐｂｏ２と
呼ばれる硬い活物質が生成して正極板の劣化を防ぐこと
ができる。Furthermore, when phosphoric acid is added to the electrolytic solution, a hard active material called αpbo2 is generated in the active material, which can prevent deterioration of the positive electrode plate.
実施例
以下、本発明による密閉式鉛蓄電池を図面を用いて説明
する。EXAMPLES Below, a sealed lead-acid battery according to the present invention will be explained with reference to the drawings.
（実施例１）
まず、Ｐｂ−Ｃａ合金からなるクラッド式正極格子を準
備した。正極板はＰｂ ｓ Ｏ４がそれぞれ５，１５゜
４０、７０．１００％で、残部ＰｂＯからなる、Ｐｂ
ｓ ０４量の興なる５種類（Ｉ〜Ｖ）の正極活物質原料
に、アンチモン粉末をそれぞれ ０．０１．０．０５．
０．１Ｇ、５，１．５％（Ｂ〜Ｇ）添加、混合した後、
上記正極格子に充填することにより製作した。なお、比
較のためにアンチモンを全く入れていない正極板Ａも製
作した。これらの正極板１枚と、ペースト六員極板２枚
およびパルプセパレータ２枚とで構成する電池を製作し
、これに希硫酸とゲル化剤とを混合した電解液を注液し
た後、所定量の充電を行ない、充電後の比重が１．３０
（２０℃）になるようにした、充電後は常法に従って安
全弁などを装着して約１０＾ｈ（５ｈＲ）容量のゲル式
電池を製作した。(Example 1) First, a clad positive electrode grid made of a Pb-Ca alloy was prepared. The positive electrode plate consists of Pb s O4 of 5, 15° 40, and 70.100%, respectively, and the balance is PbO.
Antimony powder was added to each of the five types (I to V) of positive electrode active material raw materials in an amount of 0.01.0.05.
After adding and mixing 0.1G, 5,1.5% (B to G),
It was manufactured by filling the above positive electrode grid. For comparison, a positive electrode plate A containing no antimony was also produced. A battery consisting of one of these positive electrode plates, two six-membered paste electrode plates, and two pulp separators was manufactured, and after pouring an electrolytic solution containing dilute sulfuric acid and a gelling agent into it, After a certain amount of charging, the specific gravity after charging is 1.30.
(20°C), and after charging, a safety valve etc. was attached according to the usual method, and a gel type battery with a capacity of about 10^h (5hR) was manufactured.
まず、これらの電池の放電容量（１〜目２Ａ放電持続時
間）を調べた。その結果を第１表に示す。First, the discharge capacity (1st to 2A discharge duration) of these batteries was investigated. The results are shown in Table 1.
放電容量は正極活物質中のＰｂ、 ｏ、量に比例して増
加していることがわかる。また、活物質中のアンチモン
量の多少による影響はなかった。It can be seen that the discharge capacity increases in proportion to the amount of Pb and O in the positive electrode active material. Further, there was no effect depending on the amount of antimony in the active material.
第１表
これらの電池を２．ＯＡ電流で２．５時間放電し、その
１１０％を充電する充放電サイクルを繰り返し行ない、
５００〜経過した時点で電池を解体調査した。Table 1 These batteries 2. Repeated charge/discharge cycles of discharging with OA current for 2.5 hours and charging 110% of the time,
The battery was disassembled and investigated after 500 min.
第１図に５００〜時点での放電容量（２Ａ放電持続時間
）を示す０図から明らかなように、正極活物質中のＦ’
ＤｓＯ４量が５％あるいは活物質中のアンチモン量が５
％では従来電池以下の放電容量になっていたが、ａ、０
．量が１５％以上でかつアンチモン量が０．０１〜１％
の電池では逆に従来電池以上の放電容量を維持していた
。この原因を明らかにするため解体後の正極板に針を突
き刺すことにより極板硬さを調べるとともに負極板に析
出しているアンチモン量の分析を行ない、第２表に結果
の一部を示す、なお、極板硬さは電池ＪＡを１００とし
て示した。As is clear from Figure 1, which shows the discharge capacity (2A discharge duration) from 500 to 500, F' in the positive electrode active material
The amount of DsO4 is 5% or the amount of antimony in the active material is 5%.
%, the discharge capacity was lower than that of conventional batteries, but a, 0
．． The amount of antimony is 15% or more and the amount of antimony is 0.01 to 1%.
On the contrary, this battery maintained a discharge capacity higher than that of conventional batteries. In order to clarify the cause of this, we investigated the hardness of the positive electrode plate by piercing it with a needle after disassembly, and also analyzed the amount of antimony precipitated on the negative electrode plate. Some of the results are shown in Table 2. Note that the hardness of the electrode plate is shown with battery JA as 100.
第２表
表かられかるように、ｐｂ、 ｏ、量の多い正極板でア
ンチモンを添加していないものは、著しく軟らかくなる
。一般に劣化した正極板は著′シ＜軟らかくなり活物質
は泥状化することが知られている。As can be seen from Table 2, positive electrode plates with a large amount of PB and o, to which antimony is not added, become significantly softer. It is generally known that a deteriorated positive electrode plate becomes extremely soft and the active material becomes muddy.
このことから考えて、この電池で容量が低下したのは正
極板性能が低下したためと思われる。Considering this, it seems that the reason for the decrease in capacity of this battery was due to a decrease in the performance of the positive electrode plate.
また、アンチモン添加量が５．０％と多い電池では、正
極板は硬く、良好であるが、負極板へのアンチモンの析
出量が極端に多い、この電池で容量が著しく低かったの
はアンチモンの析出による負極板性能の低下によるもの
と考えられる。In addition, in a battery with a high antimony content of 5.0%, the positive electrode plate is hard and in good condition, but the amount of antimony deposited on the negative electrode plate is extremely large.The reason why the capacity of this battery was extremely low was due to antimony. This is thought to be due to a decrease in negative electrode plate performance due to precipitation.
正極活物質へのＰ’ｂｓＯａ添加量が１５％以上でかつ
アンチモンの添加量が０．０５〜１．０％という本発明
による電池が従来電池よりも寿命性能が良かったのは正
極活物質の劣化が少なく、かつ負極板へのアンチモンの
析出量が少なかったことによるものと考えられる。The reason why the battery according to the present invention, in which the amount of P'bsOa added to the positive electrode active material is 15% or more and the amount of antimony added is 0.05 to 1.0%, had better life performance than the conventional battery is because of the positive electrode active material. This is thought to be due to the fact that there was little deterioration and the amount of antimony precipitated on the negative electrode plate was small.
（実施例２）
正極活物質原料をＰｂ、 ０．１００％とし、これにア
ンチモン粉末を０ 、０．０１．０．０５．０．１ 、
０．５ 。(Example 2) The positive electrode active material raw material was Pb, 0.100%, and antimony powder was added to it at 0%, 0.01.0.05.0.1%,
0.5.
１．０ｗｔ％添加した正極板を多数製作し、実施例１と
同じ構成で電池を製作した。A large number of positive electrode plates to which 1.0 wt% was added were manufactured, and a battery was manufactured with the same configuration as in Example 1.
注液時にリン酸を正極活物質エリ当り０，１゜１０、５
０．２００−ｇ （α〜ε）添加した。When injecting phosphoric acid per positive electrode active material area 0.1°10.5
0.200-g (α~ε) was added.
実施例１と同一の試験を行ない、１０００〜経過した時
点で電池を解体した。The same test as in Example 1 was conducted, and the battery was disassembled after 1000 min.
第２図に１０００〜後の放電容量（２Ａ放電持続時間）
を示す０図から明らかなように、リン酸の添加量が２Ｇ
Ｏ＋Ｈ／ｅａと多すぎる場合には放電容量は従来電池と
大差なかったが、５０ｍｇ／ ｅ ＩＪ以下の添加量の
場合は従来電池以上の放電容量を維持していた。Figure 2 shows the discharge capacity after 1000~ (2A discharge duration)
As is clear from Figure 0, the amount of phosphoric acid added is 2G.
When the amount was too high (O+H/ea), the discharge capacity was not much different from the conventional battery, but when the amount added was less than 50 mg/e IJ, the discharge capacity was maintained higher than that of the conventional battery.
この理由を明らかにするため、解体後の正極板に針を突
き刺して硬さを調べた。第３表にその結果の一部を示す
。To find out the reason for this, we pierced the positive electrode plate with a needle and examined its hardness after disassembly. Table 3 shows some of the results.
表から明らかなように、リン酸添加量を多くすると、正
極板は硬くなる。しかし、添加量が２００＊ａ／ｅｏと
多すぎる場合には極板が著しく硬化している。この電池
の容量が低かったのは過剰に′硬化したためと思われる
。また、第２図から、リン酸添加による効果はアンチモ
ン量が０．５％以上の場合にはあまり大きくなかったが
、これはサイクル数の増加に伴い、アンチモン量の多い
電池では負極板へのアンチモンの折忠が増加して、負極
板の性能が低下するためと思われる。As is clear from the table, when the amount of phosphoric acid added is increased, the positive electrode plate becomes harder. However, when the amount added is too large (200*a/eo), the electrode plate is significantly hardened. The low capacity of this battery is thought to be due to excessive 'curing'. Also, from Figure 2, the effect of adding phosphoric acid was not so great when the amount of antimony was 0.5% or more, but this was because as the number of cycles increased, in batteries with a large amount of antimony, the effect on the negative electrode plate was This seems to be because the amount of antimony increases and the performance of the negative electrode plate deteriorates.
第３表
また、アンチモンを正極活物質中に添加しないでも電解
液にリン酸を添加しておけば従来電池と同等以上の寿命
性能は得られたが、両者の作用は基本的には興なってお
り、両者を同時に添加するのが好ましいと思われる。Table 3 Also, if antimony was not added to the positive electrode active material but phosphoric acid was added to the electrolyte, a life performance equivalent to or higher than that of conventional batteries could be obtained, but the effects of the two are basically unaffected. Therefore, it seems preferable to add both at the same time.
なお、本実施例ではアンチモンの粉末を添加したが、ア
ンチモンの酸化物、硫化物などアンチモン化合物を添加
してもその効果は同じであった。Although antimony powder was added in this example, the effect was the same even if antimony compounds such as antimony oxides and sulfides were added.
以上の結果から、正極活物質中にｐｂ、 ｏ、を１５％
以上用いる電池において、正極活物質中にアンチモン粉
末を０．０５〜ｉ、ｏ ｗｔ％添加し、好ましくはさら
に電解液にリン酸を正極活物質１ｇ当り５０ｎｇ以下の
割合で添加すれば放電容量および寿命性能は著しく改善
されることがわかった。From the above results, 15% of PB, O, in the positive electrode active material
In the battery used above, the discharge capacity and the It was found that the life performance was significantly improved.
発明の効果
以上述べたように本発明による密閉式鉛蓄電池は従来の
密閉式鉛蓄電池に比べて放電容量およびサイクル寿命性
能が著しく優れており、その工業的価値は極めて大きい
。Effects of the Invention As described above, the sealed lead-acid battery according to the present invention has significantly superior discharge capacity and cycle life performance compared to conventional sealed lead-acid batteries, and its industrial value is extremely large.
第１図および第２図は５００〜後および１０００〜後の
放電容量を示す特性図である。FIG. 1 and FIG. 2 are characteristic diagrams showing the discharge capacity after 500 hours and after 1000 hours.
Claims (1)
格子を使用し、正極活物質中に１５％以上の鉛丹（Ｐｂ
＿３Ｏ＿４）および０．０５〜１．０ｗｔ％のアンチモ
ンあるいはアンチモン化合物の粉末を添加したことを特
徴とする密閉式鉛蓄電池。1. A positive electrode grid made of a lead alloy that does not substantially contain antimony is used, and the positive electrode active material contains 15% or more of lead (Pb).
_3O_4) and 0.05 to 1.0 wt% of antimony or antimony compound powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2077355A JP2913485B2 (en) | 1990-03-27 | 1990-03-27 | Sealed lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2077355A JP2913485B2 (en) | 1990-03-27 | 1990-03-27 | Sealed lead-acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03276561A true JPH03276561A (en) | 1991-12-06 |
| JP2913485B2 JP2913485B2 (en) | 1999-06-28 |
Family
ID=13631605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2077355A Expired - Fee Related JP2913485B2 (en) | 1990-03-27 | 1990-03-27 | Sealed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2913485B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6284411B1 (en) | 1996-10-02 | 2001-09-04 | Japan Storage Battery Co., Ltd. | Valve regulated type battery and producing method thereof |
| WO2004047201A1 (en) * | 2002-11-15 | 2004-06-03 | Gs Yuasa Corporation | Positive plate for lead storage battery and lead storage battery |
-
1990
- 1990-03-27 JP JP2077355A patent/JP2913485B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6284411B1 (en) | 1996-10-02 | 2001-09-04 | Japan Storage Battery Co., Ltd. | Valve regulated type battery and producing method thereof |
| WO2004047201A1 (en) * | 2002-11-15 | 2004-06-03 | Gs Yuasa Corporation | Positive plate for lead storage battery and lead storage battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2913485B2 (en) | 1999-06-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |