JPH03163755A - Clad type sealed lead-acid battery - Google Patents
Clad type sealed lead-acid batteryInfo
- Publication number
- JPH03163755A JPH03163755A JP1301577A JP30157789A JPH03163755A JP H03163755 A JPH03163755 A JP H03163755A JP 1301577 A JP1301577 A JP 1301577A JP 30157789 A JP30157789 A JP 30157789A JP H03163755 A JPH03163755 A JP H03163755A
- Authority
- JP
- Japan
- Prior art keywords
- positive
- pbso4
- batteries
- battery
- clad
- 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 abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008119 colloidal silica Substances 0.000 claims description 3
- 239000003349 gelling agent Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 24
- 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 description 6
- 229910052924 anglesite Inorganic materials 0.000 abstract description 6
- 239000007774 positive electrode material Substances 0.000 abstract description 6
- 238000013517 stratification Methods 0.000 abstract description 6
- 239000007773 negative electrode material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 14
- 230000005484 gravity Effects 0.000 description 11
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000007704 transition Effects 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
- H01M10/34—Gastight accumulators
- H01M10/342—Gastight lead accumulators
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- 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
本発明はクラッド式正極板とペースト式負極板を用い、
電解液にコロイダルシリカあるいはコロイダルアルミナ
等のゲル化剤を数％いれてゲル化させた希硫酸を使用す
る、いわゆるゲルクラッド式密閉形鉛電池の改良に関す
るもので、特に放電容量およびサイクル寿命性能の優れ
た密閉鉛電池を提供することを目的とするものである．
従来の技術
開放形の液式クラッド電池は、ガラスチューブに鉛粉を
充填したクラッド式極板を希ｖＡ酸中に１〜２０時間程
度浸漬《ソーキング処理）することにより、表面に約３
０〜４０％のｐｂｓｏ．を生戒させたものを用いて、極
板群を作製し、これを電槽内に収納した後、希硫酸を注
滴し、電槽内で化成することにより製造していた．ソー
キング処理を行うのは正極板表面にｐｂｓｏ．を多く生
成しておけば、化成後活物質中に活性なＰｂ０２（β−
ＰｂＯ２）が多く作られ、放電容量が増加するためであ
る．電解液にゲル状硫酸を用いる、いわゆるゲルクラッ
ド式電池は液式同様β−ｐｂｏ．を増加させるため、前
記ソーキング処理を行った正極板を使用して製造してい
た．
発明が解決しようとする課題
しかし、ゲル式密閉電池では、正極活物質中に多量のＰ
ｂＳＯａが存在すると、化成中ｐｂｓｏ．がＰｂ０２に
酸化される時に生成される硫酸が電池下部に移行してい
わゆる電解液の成層化を生じる．これは、化成の進行に
つれて電解液がゲル化していくために、液式電池のよう
に極板から発生するＨ２、０２ガスによって上記電解液
成層化を解消することはできないためである．その結果
、放電容量が少ない、あるいはサイクル寿命性能が悪い
という欠点を有していた．
課題を解決するための手段
本発明は、正極板に未化成のクラッド式極板を用いて電
槽内で化成してなるゲル式密閉形鉛電池において、未化
成の正極板のｐｂｓｏ．の割合を２０％以下にすること
により、上記問題点を解決するものである．
実總例
本発明によるゲル式電池を製作し、試験を行った．以下
に電池の製作工程と試験結果について詳述する．
まず、鉛酸化物の粉末を充填したクラッド式正極板を比
重１．１０（２０℃）の希硫酸にそれぞれ１５秒、１分
、１０分、３０分間浸漬した後、水洗乾燥した極板およ
び全く希硫酸に浸漬しない極板を用意しな．これらの極
板中のｐｂｓｏ．量を分析すると、それぞれ、約５、１
０、１５、２０、０％であった．これらのクラッド式正
極板を用いて、正極板４枚とペースト式負極板５枚とで
構戒される極板群を作製し、これを電槽内に挿入した．
次に、ゲル化剤であるコロイダルシリカと希硫酸とをあ
らかじめ混合した液を所定液量注液した後、０．２ Ｃ
Ａ （Ｃ ：公称容ｊｔ）の電流で通電することにより
化成を行った．注液した希硫酸の濃度は化成前の正極板
に含まれるｐｂｓｏ．量を考慮して決め、化成後の比重
が１．３０（２０℃〉になるようにした．
化成後安全弁等を装着して本発明による約１２０＾ｈ（
５ＨＲ））容量の電池、すなわち未化成の正極板のｐｂ
ｓｏ． ｉが異なる電池Ａ，Ｂ，Ｃ，Ｄ，Ｅを製作した
．また比較のために、希硫酸にクラッド式極板を１０時
間浸漬して、ＰｂＳＯ４量を４０％にした未化成の正極
板を用いた従来形のゲルクラッド式電池Ｆも製作した．
化成後、これらの電池の５ＨＲ放電容量を調べ、その結
果を第１図に示す．本発明による電池Ａ〜Ｅの放電容量
はいずれも従来電池Ｆよりも多く、特に未化成の正極板
中のｐｂｓｏ．量が５％および１０％の電池Ｂ，Ｃが最
も優れていた．
この理由を明らかにするため、電池の上部と下部に電解
液の比重を測定することのできるセンサーを取り付けた
．これを用いて本発明形電池Ｃと、従来形電池Ｆの化成
中の電解液比重の推移を調べた結果を第２図に、そして
本発明形電池の化成終期の電解液比重を第３図に示す．
また化成後の正極活物質中のβ−ｐｂｏ２量をＸ＠回折
試験により調べた結果を第４図に示す。[Detailed description of the invention] Industrial application field The present invention uses a clad type positive electrode plate and a paste type negative electrode plate,
This relates to the improvement of so-called gel-clad sealed lead batteries, which use dilute sulfuric acid that has been gelled by adding a few percent of a gelling agent such as colloidal silica or colloidal alumina to the electrolyte, and has particularly excellent discharge capacity and cycle life performance. The purpose is to provide a sealed lead-acid battery.
Conventional open-type liquid-type clad batteries are made by immersing a clad plate, which is a glass tube filled with lead powder, in dilute VA acid for about 1 to 20 hours (soaking treatment), so that the surface is coated with about 3.
0-40% pbso. A group of electrode plates was made using materials that had been kept in a safe condition, and after storing this in a battery case, diluted sulfuric acid was added dropwise and chemical formation was carried out inside the battery case. The soaking process is performed by applying pbso. If a large amount of Pb02 (β-
This is because a large amount of PbO2) is produced and the discharge capacity increases. The so-called gel clad type battery, which uses gelled sulfuric acid as the electrolyte, has a β-pbo. In order to increase this, the positive electrode plate was manufactured using the soaking treatment described above. Problems to be Solved by the Invention However, in gel-type sealed batteries, a large amount of P is present in the positive electrode active material.
When bSOa is present, pbso. The sulfuric acid produced when Pb02 is oxidized to Pb02 migrates to the bottom of the battery, causing so-called stratification of the electrolyte. This is because the electrolyte gels as the chemical formation progresses, so the electrolyte stratification cannot be eliminated by the H2, 02 gas generated from the electrode plates as in a liquid type battery. As a result, they had the drawbacks of low discharge capacity and poor cycle life performance. Means for Solving the Problems The present invention provides a gel-type sealed lead-acid battery in which an unchemically formed clad type electrode plate is used as a positive electrode plate and chemically formed in a battery case, in which a pbso. The above problem is solved by reducing the ratio to 20% or less. Practical Example A gel battery according to the present invention was manufactured and tested. The battery manufacturing process and test results are detailed below. First, a clad positive electrode plate filled with lead oxide powder was immersed in dilute sulfuric acid with a specific gravity of 1.10 (20°C) for 15 seconds, 1 minute, 10 minutes, and 30 minutes, respectively. Prepare electrode plates that will not be immersed in dilute sulfuric acid. pbso. in these plates. Analyzing the amount, it is about 5 and 1, respectively.
They were 0, 15, 20, and 0%. Using these clad-type positive electrode plates, a plate group consisting of four positive plates and five paste-type negative plates was prepared, and this was inserted into a battery case. Next, after injecting a predetermined amount of a premixed solution of colloidal silica, which is a gelling agent, and dilute sulfuric acid, 0.2C
Chemical formation was performed by applying a current of A (C: nominal capacity jt). The concentration of the injected dilute sulfuric acid is PBSO. The specific gravity after chemical formation was determined to be 1.30 (at 20°C). After chemical formation, a safety valve, etc. was installed, and the temperature of about 120 hours (
5HR)) capacity battery, i.e. unformed positive plate pb
so. Batteries A, B, C, D, and E with different i were manufactured. For comparison, we also fabricated a conventional gel-clad battery F using an unformed positive electrode plate with a PbSO4 content of 40% by immersing the clad plate in dilute sulfuric acid for 10 hours.
After chemical formation, the 5HR discharge capacity of these batteries was investigated, and the results are shown in Figure 1. The discharge capacities of the batteries A to E according to the present invention are all higher than that of the conventional battery F, especially the pbso. Batteries B and C with a content of 5% and 10% were the best. In order to clarify the reason for this, we installed sensors that can measure the specific gravity of the electrolyte at the top and bottom of the battery. Figure 2 shows the results of examining the changes in electrolyte specific gravity during formation of the battery of the present invention C and conventional battery F using this, and Figure 3 shows the specific gravity of the electrolyte at the end of the formation of the battery of the invention. It is shown in
In addition, FIG. 4 shows the results of examining the amount of β-pbo2 in the positive electrode active material after chemical formation by an X@ diffraction test.
従来形電池Ｆは、化成初期から電池上部（Ｆ−上）と下
部（Ｆ一下）における電解液比重差があり、化成がさら
に進行してもその比重差は解消されず、逆に広がってゆ
く傾向があった．一方、本発明形電池Ｃは、化成初期か
ら上部（Ｃ一上）と下部（Ｃ一下）の電解液比重差はな
く、化成が進行しても、それほど比重差は広がらなかっ
た．これは本発明電池の正極末化板中のｐｂＳＯ，量が
従来形電池Ｆに比べて少ないため正極板から極板の外に
排出されるＩ２ＳＯＡ量が少なかったためと考えられる
．Ｃ以外の本発明電池でも化成終期の電解液の成層化は
従来電池Ｆよりもかなり少なく、初期性能が従来電池よ
りもかなり良かったのはこのためと思われる．
また、本発明電池Ａ〜Ｅを比較すると、未化成の正極板
中のｐｂｓａ．量が少なくなるほど化成後の電解液の成
層化は少なくなったが、化成後のβ−Ｐｂ０２量も少な
かった．本発明電池のうちｐｂｓｏ．量が５％あるいは
１０％の電池Ｂ，Ｃの容量が最も良かったのは、電解液
の成層化が少なく、β−ｐｂｏ２量が多かったためと思
われる．
次に、これらの電池を放電深さ７５％の充放電サイクル
試験に供した．このときのサイクル中の容量推移を第５
図に示す．本発明電池はいずれも従来電池Ｆよりも寿命
性能が著しくすぐれており、特に未化成の正極板中のｐ
ｂｓｏ．量が少ない電池ほど寿命性能がすぐれていた．
これは、電解液の成層化が少ないものほど正、負極活物
質が均一に充・放電をうけることができるためと思われ
る．発明の効果
以上述べたように、本発明によるゲルクラッド式密閉形
鉛電池は、従来のゲルクラッド式密閉形鉛電池に比べて
、放電容量およびサイクル寿命性能が著しくすぐれてお
り、その工業的価値は極めて大きい。In conventional battery F, there is a difference in the specific gravity of the electrolyte between the upper part of the battery (F-upper) and the lower part (F-lower) from the beginning of formation, and even as formation progresses further, this difference in specific gravity does not disappear and instead widens. There was a tendency. On the other hand, in the battery C of the present invention, there was no difference in the specific gravity of the electrolyte between the upper part (C1 upper) and the lower part (C1 lower) from the early stage of chemical formation, and even when chemical formation progressed, the specific gravity difference did not increase much. This is thought to be because the amount of pbSO in the positive electrode terminal plate of the battery of the present invention was smaller than that of conventional battery F, so the amount of I2SOA discharged from the positive electrode plate to the outside of the electrode plate was small. In the batteries of the present invention other than C, the stratification of the electrolyte at the end of chemical formation was considerably less than in conventional battery F, which is probably why the initial performance was much better than that of conventional batteries. Comparing Batteries A to E of the present invention, pbsa. As the amount decreased, the stratification of the electrolytic solution after chemical formation decreased, but the amount of β-Pb02 after chemical formation also decreased. Among the batteries of the present invention, pbso. The reason why batteries B and C with a concentration of 5% or 10% had the best capacity is probably due to less stratification of the electrolyte and a higher amount of β-pbo2. Next, these batteries were subjected to a charge/discharge cycle test at a discharge depth of 75%. The capacity transition during the cycle at this time is shown in the fifth column.
It is shown in the figure. All of the batteries of the present invention have significantly superior life performance than conventional battery F, and in particular, the p
bso. Batteries with lower capacity had better life performance.
This seems to be because the less stratified the electrolyte is, the more uniformly the positive and negative electrode active materials can be charged and discharged. Effects of the Invention As mentioned above, the gel-clad sealed lead-acid battery according to the present invention has significantly superior discharge capacity and cycle life performance compared to conventional gel-clad sealed lead-acid batteries, and its industrial value is extremely high. big.
第１図は化成後の放電容量を示す特性図、第２図は化成
中の電池上部と下部の電解液比重の推移を示す特性図、
第３図は化成終期の電池上部と下部の電解液比重を示す
特性図、第４図は化成後の正極活物質中のβ−Ｐｂ０２
量を示す特性図、第５図は充放電サイクル試験中の放電
容量の推移を示す特性図である。
弟２１の
Ｆ−″下
イヒ森８＋回
Ｃｈ−）
電；ヒ Ａ
ＰｂＳ晴（ｏ１ｏ） ０
Ｂ（；−Ｅ）ｐＦ
５ｌθ １夕 ２０４０
遍
タ
ｔＶ
イ乙７（宅サイクノＵ食（Figure 1 is a characteristic diagram showing the discharge capacity after formation, Figure 2 is a characteristic diagram showing changes in the specific gravity of the electrolyte in the upper and lower parts of the battery during formation.
Figure 3 is a characteristic diagram showing the specific gravity of the electrolyte in the upper and lower parts of the battery at the final stage of chemical formation, and Figure 4 is the β-Pb02 in the positive electrode active material after chemical formation.
FIG. 5 is a characteristic diagram showing the change in discharge capacity during a charge/discharge cycle test. Younger brother 21's F-''Shimoihi Mori 8+ times Ch-) Electric; Hi A PbS Haru (o1o) 0 B (;-E) pF 5lθ 1 evening 2040 Henta tV Iotsu 7 (Taku Saiku no U food (
Claims (1)
極板とを用い、電解液にコロイダルシリカあるいはコロ
イダルアルミナ等のゲル化剤を数％入れてゲル化させた
希硫酸を使用し、電槽内で化成を行なったゲルクラッド
式密閉形鉛電池において、該未化成板中の硫酸鉛の割合
を２０％以下にしたことを特徴とするクラッド式密閉形
鉛電池。1. Using an unformed clad positive electrode plate and an unformed paste negative electrode plate, use dilute sulfuric acid that has been gelled by adding a few percent of a gelling agent such as colloidal silica or colloidal alumina to the electrolyte. A gel-clad sealed lead battery which is chemically formed in a tank, characterized in that the proportion of lead sulfate in the unformed plate is 20% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1301577A JPH03163755A (en) | 1989-11-20 | 1989-11-20 | Clad type sealed lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1301577A JPH03163755A (en) | 1989-11-20 | 1989-11-20 | Clad type sealed lead-acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03163755A true JPH03163755A (en) | 1991-07-15 |
Family
ID=17898621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1301577A Pending JPH03163755A (en) | 1989-11-20 | 1989-11-20 | Clad type sealed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03163755A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7682738B2 (en) | 2002-02-07 | 2010-03-23 | Kvg Technologies, Inc. | Lead acid battery with gelled electrolyte formed by filtration action of absorbent separators and method for producing it |
-
1989
- 1989-11-20 JP JP1301577A patent/JPH03163755A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7682738B2 (en) | 2002-02-07 | 2010-03-23 | Kvg Technologies, Inc. | Lead acid battery with gelled electrolyte formed by filtration action of absorbent separators and method for producing it |
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