JPH0443550A - Sealed lead-acid battery - Google Patents
Sealed lead-acid batteryInfo
- Publication number
- JPH0443550A JPH0443550A JP2152022A JP15202290A JPH0443550A JP H0443550 A JPH0443550 A JP H0443550A JP 2152022 A JP2152022 A JP 2152022A JP 15202290 A JP15202290 A JP 15202290A JP H0443550 A JPH0443550 A JP H0443550A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- film
- electrode plate
- sealed lead
- acid battery
- 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 claims abstract description 20
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 9
- 239000000155 melt Substances 0.000 claims abstract description 8
- 229920013716 polyethylene resin Polymers 0.000 claims abstract description 5
- 239000004705 High-molecular-weight polyethylene Substances 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000010998 test method Methods 0.000 claims description 2
- 229920006262 high density polyethylene film Polymers 0.000 abstract description 13
- 239000004698 Polyethylene Substances 0.000 abstract description 10
- 229920001903 high density polyethylene Polymers 0.000 abstract description 5
- 239000004700 high-density polyethylene Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- -1 polyethylene Polymers 0.000 abstract 1
- 229920000573 polyethylene Polymers 0.000 abstract 1
- 239000000463 material Substances 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- Sealing Battery Cases Or Jackets (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、ポータプル機器用として多方面に利用され、
とくにＶＴＲ用電源などに使用されている密閉形鉛蓄電
池に関し、とくにその極板に接する熱可塑性樹脂の改良
に関する。[Detailed Description of the Invention] Industrial Application Fields The present invention can be used in various fields as a portable device.
In particular, the present invention relates to sealed lead-acid batteries used in power sources for VTRs, and particularly to improvements in the thermoplastic resin that is in contact with the electrode plates.
従来の技術
密閉形鉛蓄電池は、従来鉛蓄電池の中で主流であった自
動車用などとは用途が異なるため、その構造、使用材料
も異なっているため、多くの新しい提案がなされ、その
性能も著しく向上してきている。従来この種の密閉形鉛
蓄電池は、性極板、負極板およびセパレータからなる極
板群の両面を覆う熱可塑性樹脂フィルムとして、加工性
、枠体との熱溶着性、機械的強度および耐熱性の優れた
高密度ポリエチレン樹脂（）（ＤＰＥ）およびその変性
体が用いられている。その代表的な物理的性質として、
平均分子量が５万、融点１２０〜１３０℃、メルトイン
デックス５〜１０ （ｇ／１０ｍ１ｎ）で、Ｔダイ法な
どで容易に厚さ３０μ以上のフィルムを作ることが可能
である。Conventional technology Sealed lead-acid batteries are used for different purposes, such as those for automobiles, which have been the mainstream among conventional lead-acid batteries, and their structures and materials used are also different. Therefore, many new proposals have been made, and their performance has also improved. It has improved significantly. Conventionally, this type of sealed lead-acid battery is made of a thermoplastic resin film that covers both sides of the electrode plate group consisting of a positive electrode plate, a negative electrode plate, and a separator. High-density polyethylene resin (DPE) and its modified products are used. As its representative physical properties,
It has an average molecular weight of 50,000, a melting point of 120 to 130°C, and a melt index of 5 to 10 (g/10 m1n), and can easily be made into a film with a thickness of 30 μm or more using the T-die method.
発明が解決しようとする課題
しかし、このような性質のＨＤＰＥフィルムを用いた密
閉形鉛蓄電池では、高温で長期間使用すると電池内より
発生する活性な酸素や、正極板の活物質である酸化性の
強い二酸化鉛により、ＨＤＰＥフィルムの一部が分解さ
れてクラックを生じ、このクラックが枠体との溶着面に
達すると電池の密閉性が保てなくなり、電池としての性
能が劣化するケースがある。Problems to be Solved by the Invention However, in sealed lead-acid batteries using HDPE films with such properties, active oxygen generated from within the battery when used at high temperatures for long periods of time, and oxidizing active material of the positive electrode plate. Due to the strong lead dioxide, part of the HDPE film decomposes and cracks occur, and if these cracks reach the welded surface with the frame, the battery may no longer be able to maintain its airtightness, resulting in deterioration of battery performance. .
このため、と（に機器に内蔵され電池温度が上昇しやす
いトリクル充電されるような使用条件では従来のＡＢＳ
樹脂電槽を用いた電池より、電解液の水分蒸発による容
量低下が少ないのにもかかわらず、電池の寿命特性が短
くなるという問題点があった。For this reason, conventional ABS
Although the capacity decrease due to evaporation of water in the electrolyte is smaller than batteries using resin containers, there is a problem in that the battery life characteristics are shortened.
本発明は、上記問題点を解決するため、ＨＤＰＥフィル
ム材質に耐酸化性、耐酸性の優れた材質を用いることに
より、高温使用においても長寿命の密閉形鉛蓄電池を提
供することを目的とする。In order to solve the above-mentioned problems, the present invention aims to provide a sealed lead-acid battery that has a long life even when used at high temperatures by using a material with excellent oxidation resistance and acid resistance for the HDPE film material. .
課題を解決するための手段
この課題を解決するため本発明の密閉形鉛蓄電池は、Ｈ
ＤＰＥフィルムの一部に分子量１０万〜１００万の高分
子量ポリエチレンを配合し、かつフィルムとしての加工
性を得るため低分子量成分を含みメルトインデックス０
．１〜１．５（ｇ ／ １０ ｍ ｉ ｎ ）のＨＤＰ
Ｅフィルムを用いるものである。Means for Solving the Problem In order to solve this problem, the sealed lead acid battery of the present invention has H
High molecular weight polyethylene with a molecular weight of 100,000 to 1,000,000 is blended into a part of the DPE film, and in order to obtain processability as a film, it contains low molecular weight components and has a melt index of 0.
．． 1-1.5 (g/10 min) HDP
It uses E film.
作用
この構成により本発明の密閉形鉛蓄電池は高温で使用し
ても分子量１０〜１００万の高分子量ポリエチレンを配
合し、加工性をうるためにメルトインデックスを０．１
〜０．５ ［ｇ／１０ｍ１ｎ］として、耐酸化性を向上
したＨＤＰＥフィルムを使用することによりそのクラッ
ク発生を防止できることなる。Function: Due to this structure, the sealed lead-acid battery of the present invention is formulated with high molecular weight polyethylene having a molecular weight of 100,000 to 1,000,000 even when used at high temperatures, and has a melt index of 0.1 in order to obtain processability.
~0.5 [g/10m1n], by using an HDPE film with improved oxidation resistance, it is possible to prevent the occurrence of cracks.
実施例
以下、本発明の一実施例の密閉形鉛蓄電池について、第
１図を参照して説明する。第１図は、本実施例で試作し
た密閉形鉛蓄電池を示すもので、正極板１．負極板２お
よびセパレータ３よりなる極板群４の両面を覆うＨＤＰ
Ｅフィルム５を極板群４の接する面にラミネートした金
属板６と、極板群４の周囲を囲み排気弁８を備えポリエ
チレン樹脂などよりなる枠体７を溶着し封口する構成に
なっている。この電池において、金属板６にラミネート
されたＨＤＰＥフィルム５の材質を変更し、６０℃、２
．３／セルのトリクル充電を３ケ月間実施し、１５日ご
とに電池の気密性を確認するとともに、３ケ月間トリク
ル充電を終了した電池を分解してクラック発生の有無を
確認した。EXAMPLE Hereinafter, a sealed lead-acid battery according to an example of the present invention will be described with reference to FIG. FIG. 1 shows a sealed lead-acid battery prototyped in this example. HDP covering both sides of the electrode plate group 4 consisting of the negative electrode plate 2 and the separator 3
A metal plate 6 on which E film 5 is laminated on the surface in contact with the electrode plate group 4 and a frame 7 made of polyethylene resin or the like surrounding the electrode plate group 4 and equipped with an exhaust valve 8 are welded and sealed. . In this battery, the material of the HDPE film 5 laminated to the metal plate 6 was changed, and the material was
．． 3/ Cells were trickle charged for three months, and the airtightness of the batteries was checked every 15 days, and the batteries that had been trickle charged for three months were disassembled to check for cracks.
（以 下 余 白）
ＨＤＰＥフィルム５は、表に示したように、Ａは平均分
子量５万のＨＤＰＥのみのフィルム、Ｂは平均分子量１
０万の高分子量ＰＥをＡに配合したＨＤＰＥフィルム、
Ｃは平均分子量２０万の高分子量ＰＥをＡに配合したＨ
ＤＰＥフィルム、Ｄは平均分子量５０万の高分子量ＰＥ
をＡに配合したＨＤＰＥフィルム、同じくＥは、平均分
子量８０万の高分子量ＰＥをＡに配合したＨＤＰＥフィ
ルムの５種類について評価した。(Left below) HDPE film 5 is, as shown in the table, A is a film made only of HDPE with an average molecular weight of 50,000, and B is a film made only of HDPE with an average molecular weight of 1.
HDPE film containing A with 00,000 high molecular weight PE,
C is H which is a mixture of A with high molecular weight PE with an average molecular weight of 200,000.
DPE film, D is high molecular weight PE with an average molecular weight of 500,000
Five types of HDPE films were evaluated: A was blended with A, and E was a HDPE film in which A was blended with high molecular weight PE having an average molecular weight of 800,000.
なお、高分子量ＰＥは、分子が大きく融けた状態でも流
動性が悪いので、高分子量ＰＥの配合量は、Ｔダイ法に
よって厚さ５０μＨＤＰＥフイルムを形成できる程度の
流動性を有する量にコントロールし、その時のメルトイ
ンデックス（ＭＩ）をＡＳＴＭ試験法Ｄ１２３８により
測定した。In addition, since high molecular weight PE has poor fluidity even when the molecules are large and molten, the amount of high molecular weight PE blended is controlled to an amount that has enough fluidity to form a 50μ thick HDPE film by the T-die method. The melt index (MI) at that time was measured according to ASTM test method D1238.
このメルトインデックス（Ｍ Ｉ ）は、平均分子量に
よって決定され、平均分子量が大きいとＭｌは小さくな
り、耐ストレスクラツキング性が向上するので、Ｍｌを
フィルム形成できる範囲で低く抑さえることが望ましい
。This melt index (M I ) is determined by the average molecular weight, and as the average molecular weight becomes larger, Ml becomes smaller and stress cracking resistance improves, so it is desirable to keep Ml as low as possible to form a film.
その結果、配合する高分子量ＰＥの平均分子量が１０万
以上で、クラック発生防止に効果があり、その平均分子
量の高いほどその効果が大きい傾向を示したが、平均分
子量が高いとフィルム製造時の溶けた樹脂の流動性が低
下しフィルム形成が困難になるので、メルトインデック
スは、０．１〜１．５ （ｇ／１０ｍ１ｎ）必要であり
、平均分子量１００万が上限である。As a result, it was found that when the average molecular weight of the high molecular weight PE to be blended is 100,000 or more, it is effective in preventing crack generation, and the higher the average molecular weight, the greater the effect. Since the fluidity of the melted resin decreases and film formation becomes difficult, a melt index of 0.1 to 1.5 (g/10 m1n) is required, and the upper limit is an average molecular weight of 1 million.
発明の効果
以上の実施例の説明で明らかなように、本発明の密閉形
鉛蓄電池によれば、高温で長期間放置あるいは、トリク
ル充電しても、フィルムのクラックによる密閉性の低下
が生じないので、長寿命で信頼性の高い密閉形鉛蓄電池
を提供することができる。この理由として次のことが考
えられる。Effects of the Invention As is clear from the description of the embodiments above, according to the sealed lead acid battery of the present invention, even if it is left at high temperatures for a long period of time or trickle charged, the sealing performance does not deteriorate due to cracks in the film. Therefore, it is possible to provide a sealed lead-acid battery with a long life and high reliability. The following may be the reason for this.
一般のＨＤＰＥフィルムは、高温になるとその分子が結
晶化しやすいため、と（に酸化雰囲気などでは、分子の
一部が酸化されてクラックを生じやすいが、ＨＤＰＥの
分子鎖間に高分子量ＰＥの大きな分子鎖を取り入れると
、結晶化によるクラック発生を防止するとともに、ＨＤ
ＰＥ分子間を結合させる機能があると考えられる。In general HDPE films, the molecules tend to crystallize at high temperatures, so in an oxidizing atmosphere, some of the molecules are easily oxidized and cracks occur. Incorporating molecular chains prevents cracks caused by crystallization and improves HD
It is thought that it has a function of binding PE molecules.
上述のように、本発明の密閉形鉛蓄電池は、高温で使用
されても密閉の信頼性が高く、また金属板やＰＥ枠体で
電槽を構成しているので、電解液の水分蒸発による容量
劣化も一般的なＡＢＳ樹脂電槽に比べて少なく、極板群
自体の長寿命化も可能であり、その工業的価値は極めて
大きい。As mentioned above, the sealed lead-acid battery of the present invention has high sealing reliability even when used at high temperatures, and since the battery case is composed of metal plates and PE frames, it is difficult to prevent moisture from evaporating from the electrolyte. Capacity deterioration is also less than that of general ABS resin battery containers, and the life of the electrode plate group itself can be extended, so its industrial value is extremely large.
第１図は本発明の一実施例による密閉形鉛蓄電池の構成
を示す分解斜視図である。
１・・・・・・正極板、２・・・・・・負極板、３・・
・・・・セパレータ、４・・・・・・極板群、５・・・
・・・熱可塑性樹脂フィルム、６・・・・・・金属板、
７・・・・・・枠体。
代理人の氏名 弁理士 粟野重孝 はか１冬用
図
正極）反
ｓｖＪ版
じ）（Ｌ−夕
梧様町
一本〜可秀りシ丁不参丁月りフィＩＬム奮晃級
Ｊこ１−イ４くFIG. 1 is an exploded perspective view showing the structure of a sealed lead-acid battery according to an embodiment of the present invention. 1... Positive electrode plate, 2... Negative electrode plate, 3...
... Separator, 4 ... Plate group, 5 ...
...Thermoplastic resin film, 6...Metal plate,
7...Frame body. Name of Agent: Patent Attorney Shigetaka Awano -I4
Claims (3)
と、この極板群の両面に位置する熱可塑性樹脂フィルム
または熱可塑性樹脂フィルムをラミネートした金属板と
、前記極板群の側面周囲を包囲する熱可塑性樹脂枠体を
備えた構造の鉛蓄電池であって、前記熱可塑性樹脂フィ
ルムが高分子量ポリエチレン樹脂を含有する密閉形鉛蓄
電池。(1) An electrode plate group consisting of a positive electrode plate, a negative electrode plate, and a separator, a thermoplastic resin film or a metal plate laminated with a thermoplastic resin film located on both sides of this electrode plate group, and a side surface of the electrode plate group. A sealed lead acid battery having a structure including a surrounding thermoplastic resin frame, the thermoplastic resin film containing a high molecular weight polyethylene resin.
〜１００万である請求項１記載の密閉形鉛蓄電池。(2) The sealed lead-acid battery according to claim 1, wherein the high molecular weight polyethylene resin has an average molecular weight of 100,000 to 1,000,000.
脂フィルムのメルトインデックスが０．１〜１．５〔ｇ
／１０ｍｉｎ〕（ＡＳＴＭ試験法Ｄ１２３８）である請
求項１記載の密閉形鉛蓄電池。(3) The melt index of the thermoplastic resin film containing high molecular weight polyethylene resin is 0.1 to 1.5 [g]
/10min] (ASTM test method D1238).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2152022A JP2926903B2 (en) | 1990-06-11 | 1990-06-11 | Sealed lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2152022A JP2926903B2 (en) | 1990-06-11 | 1990-06-11 | Sealed lead-acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0443550A true JPH0443550A (en) | 1992-02-13 |
| JP2926903B2 JP2926903B2 (en) | 1999-07-28 |
Family
ID=15531351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2152022A Expired - Fee Related JP2926903B2 (en) | 1990-06-11 | 1990-06-11 | Sealed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2926903B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5524842A (en) * | 1993-09-10 | 1996-06-11 | Nsk Ltd. | Retractor with a clamp mechanism |
| US5588611A (en) * | 1994-03-10 | 1996-12-31 | Nsk Ltd. | Retractor with a clamping mechanism |
| US5588609A (en) * | 1994-04-13 | 1996-12-31 | Nsk Ltd. | Seat belt winding device |
| US5678782A (en) * | 1994-12-27 | 1997-10-21 | Nsk Ltd. | Retractor having a clamp |
-
1990
- 1990-06-11 JP JP2152022A patent/JP2926903B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5524842A (en) * | 1993-09-10 | 1996-06-11 | Nsk Ltd. | Retractor with a clamp mechanism |
| US5588611A (en) * | 1994-03-10 | 1996-12-31 | Nsk Ltd. | Retractor with a clamping mechanism |
| US5588609A (en) * | 1994-04-13 | 1996-12-31 | Nsk Ltd. | Seat belt winding device |
| US5678782A (en) * | 1994-12-27 | 1997-10-21 | Nsk Ltd. | Retractor having a clamp |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2926903B2 (en) | 1999-07-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |