JP2768197B2 - Sealed storage battery - Google Patents
Sealed storage batteryInfo
- Publication number
- JP2768197B2 JP2768197B2 JP5030005A JP3000593A JP2768197B2 JP 2768197 B2 JP2768197 B2 JP 2768197B2 JP 5030005 A JP5030005 A JP 5030005A JP 3000593 A JP3000593 A JP 3000593A JP 2768197 B2 JP2768197 B2 JP 2768197B2
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- holder
- battery
- silica gel
- inorganic powder
- 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.)
- Expired - Fee Related
Links
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
- Cell Separators (AREA)
- Secondary Cells (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は密閉形蓄電池に関するも
のであり、特にペースト式極板と電解液保持体との界面
部における電解液の成層化防止の技術に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealed storage battery, and more particularly to a technique for preventing a stratification of an electrolyte at an interface between a paste-type electrode plate and an electrolyte holder.
【０００２】[0002]
【従来の技術】密閉形鉛蓄電池等の密閉形蓄電池は、電
解液保持体を間に介してペースト式極板が積層された極
板群が電槽内に配置されて構成されており、極板群は電
槽により電解液保持体とペースト式極板とが密着するよ
うに所定の圧力で積層方向に加圧されている。この種の
電池では充電時に陽極板から発生する酸素ガスを陰極板
に吸収させて、陰極板からの水素ガスの発生を抑制する
ため、酸素ガスが通過しやすい微細な径のガラス繊維や
合成繊維の不織布からなるリテーナを電解液保持体とし
て用いている。しかしながら、単にリテーナを電解液保
持体として用いた電池では、酸素ガスは通過しやすいも
のの、電池に充放電を繰り返すうちに電解液保持体の上
部の電解液濃度が低下し、下部の電解液濃度が高くなる
といういわゆる成層化現象が起きる。特に極板と電解液
保持体との界面部において成層化現象が起きると、電池
の充放電反応が局部的になるため、電池の容量が低下し
て、電池の寿命が短くなるという問題がある。そこで、
電槽から極板群にかかる圧力を高めて極板と電解液保持
体との密着性を高めたり、ガラス繊維の不織布に電解液
を保持する無機物粉体を含有させた無機物粉体含有リテ
ーナを電解液保持体として用いることが提案された。無
機物粉体は、複雑な細孔構造を有しており、また電解液
との親和力が高いため、電解液保持体の電解液保持力を
高めて、成層化を防止する。2. Description of the Related Art A sealed storage battery such as a sealed lead storage battery has a structure in which an electrode group in which paste-type electrode plates are laminated with an electrolyte holder interposed therebetween is arranged in a battery case. The plate group is pressed in a stacking direction at a predetermined pressure by a battery case so that the electrolyte holder and the paste electrode plate are in close contact with each other. In this type of battery, oxygen gas generated from the anode plate during charging is absorbed by the cathode plate, and the generation of hydrogen gas from the cathode plate is suppressed. Is used as the electrolyte holder. However, in a battery that simply uses a retainer as an electrolyte holder, although the oxygen gas easily passes, the concentration of the electrolyte in the upper portion of the electrolyte holder decreases as the battery is repeatedly charged and discharged, and the concentration of the electrolyte in the lower portion decreases. The so-called stratification phenomenon occurs in which the temperature increases. In particular, when a stratification phenomenon occurs at the interface between the electrode plate and the electrolyte holder, the charge / discharge reaction of the battery is localized, so that the capacity of the battery is reduced and the life of the battery is shortened. . Therefore,
Increase the pressure applied to the electrode group from the battery case to increase the adhesion between the electrode plate and the electrolyte holder, or use an inorganic powder-containing retainer that contains an inorganic powder that holds the electrolyte in a nonwoven glass fiber fabric. It has been proposed for use as an electrolyte holder. The inorganic powder has a complicated pore structure and a high affinity for the electrolyte, so that the electrolyte holding force of the electrolyte holder is increased to prevent stratification.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、前者の
ように極板群に加える圧力を高めるには、電槽の強度を
高めなければならないという問題がある。また、後者の
ように無機物粉体含有リテーナを電解液保持体として用
いた場合には、無機物粉体の量が多くなるほど、無機物
粉体の凝集により電解液保持体が硬くなり、いわゆる電
解液保持体と極板とのなじみが悪くなる。そのため、電
解液保持体と極板との間に隙間ができて、隙間に滞留す
る電解液が成層化して電池の容量及び寿命が低下すると
いう問題があった。However, in order to increase the pressure applied to the electrode plate group as in the former case, there is a problem that the strength of the battery case must be increased. In addition, when the inorganic powder-containing retainer is used as the electrolyte holder as in the latter, as the amount of the inorganic powder increases, the electrolyte holder becomes harder due to agglomeration of the inorganic powder. Familiarity between the body and the electrode plate gets worse. Therefore, there is a problem that a gap is formed between the electrolyte holder and the electrode plate, and the electrolyte staying in the gap is stratified, and the capacity and life of the battery are reduced.
【０００４】本発明の目的は、ペースト式極板と無機物
粉体を含有する電解液保持体との界面部における電解液
の成層化を防止できる密閉形蓄電池を提供することにあ
る。[0004] It is an object of the present invention to provide a sealed battery capable of preventing the stratification of the electrolyte at the interface between the paste-type electrode plate and the electrolyte holder containing inorganic powder.
【０００５】[0005]
【課題を解決するための手段】請求項１の発明では、電
解液を保持する無機物粉体を含有する電解液保持体を間
に介在させてペースト式極板を積層してなる極板群を有
する密閉形蓄電池を対象にして、電解液保持体にシリカ
ゲル繊維を含有させる。According to the first aspect of the present invention, there is provided an electrode group formed by laminating paste electrode plates with an electrolyte holder containing an inorganic powder for holding an electrolyte interposed therebetween. For a sealed storage battery having the same, the electrolyte solution holder contains silica gel fibers.
【０００６】請求項２の発明では、無機物粉体の電解液
保持体に対する重量比を２０〜８０％とし、シリカゲル
繊維の電解液保持体に対する重量比を２〜３％とする。According to the second aspect of the present invention, the weight ratio of the inorganic powder to the electrolyte holder is 20 to 80%, and the weight ratio of the silica gel fiber to the electrolyte holder is 2 to 3%.
【０００７】[0007]
【作用】請求項１の発明のように電解液保持体にシリカ
ゲル繊維を含有させると、シリカゲル繊維の一部が電解
液中に溶解して電解液がある程度の粘性を持つようにな
る。シリカゲル繊維の一部が溶解すると、電解液保持体
を構成する繊維間の結合力と無機物粉体間の凝集力が弱
くなって電解液保持体がほぐれる。その結果、電解液保
持体と極板との間の密着性が高まり、極板と電解液保持
体との界面における電解液の成層化を抑制して、電池の
容量を高め、寿命を延ばすことができる。また本発明に
よれば、シリカゲル繊維により電解液の粘性が高くなる
ことによっても電解液の成層化を抑制することができ
る。When the silica gel fiber is contained in the electrolyte holder as in the first aspect of the present invention, a part of the silica gel fiber dissolves in the electrolyte and the electrolyte has a certain viscosity. When a part of the silica gel fiber is dissolved, the bonding force between the fibers constituting the electrolyte holder and the cohesive force between the inorganic powders are weakened, and the electrolyte holder is loosened. As a result, the adhesion between the electrolyte holder and the electrode plate is increased, the stratification of the electrolyte at the interface between the electrode plate and the electrolyte holder is suppressed, the capacity of the battery is increased, and the life is extended. Can be. Further, according to the present invention, stratification of the electrolytic solution can be suppressed by increasing the viscosity of the electrolytic solution by the silica gel fiber.
【０００８】電解液保持体に対する無機物粉体及びシリ
カゲル繊維の重量比を請求項２の発明に示す範囲にする
と、極板と電解液保持体との界面部における電解液の成
層化を有効に防止することができる。シリカゲル繊維の
重量比が２％を下回ると電解液保持体を十分にほぐすこ
とができないので、電解液の成層化を十分に防止するこ
とができない。またシリカゲル繊維の重量比が３％を上
回ると電解液保持体のほぐれが大きくなりすぎ、電解液
保持体が電解液を保持し難くなる。When the weight ratio of the inorganic powder and the silica gel fiber to the electrolyte holder is set in the range described in the second aspect of the present invention, stratification of the electrolyte at the interface between the electrode plate and the electrolyte holder is effectively prevented. can do. If the weight ratio of the silica gel fiber is less than 2%, the electrolyte holding member cannot be sufficiently loosened, so that stratification of the electrolyte cannot be sufficiently prevented. On the other hand, if the weight ratio of the silica gel fiber exceeds 3%, the looseness of the electrolyte holder becomes too large, and it becomes difficult for the electrolyte holder to hold the electrolyte.
【０００９】[0009]
【実施例】以下、本発明を密閉形鉛蓄電池に適用した実
施例について図面を参照して詳細に説明する。本実施例
の密閉形鉛蓄電池は次のようにして作った。まずＳｉ
（ＯＣ2 Ｈ5 ）4 を２０重量％含む水溶液を攪拌しなが
ら該溶液にＳｉ（ＯＣ2 Ｈ5 ）4 に対する割合が１重量
％の硫酸を徐々に加え、溶液の粘度が１０poise 以上に
なったところで、この溶液をノズルを通して引張るゾル
ゲル法により平均線径４μm のシリカゲル繊維を作っ
た。次に長さ２mmにしたこのシリカゲル繊維２重量％
と、平均粒径１０〜３０ｎｍのＳｉＯ2 粉体５０重量％
と平均粒径５〜７０μｍのケイソウ土５０重量％とから
なる無機物粉体２０重量％と、長さ２mmにした線径０．
７μm のガラス繊維と、ポリアミドアクリルアミドから
なる無機粉体の吸着剤０．５重量％とを純水で分散した
ものを抄造してから乾燥し、厚み２．４mmの不織布状の
電解液保持体を作った。尚、電解液保持体は全体として
の重量比表面積が２０〜８０ m2 /gとなるのが好まし
い。シリカゲル繊維の電解液保持体全体に対する好まし
い添加量は２〜３重量％であり、無機物粉体の電解液保
持体全体に対する好ましい添加量は２０〜８０重量％で
ある。次にこの電解液保持体を間に介在させて公知のペ
ースト式正極板（高さ２４０mm×幅１４０mm）８枚と公
知のペースト式負極板（高さ２４０mm×幅１４０mm）９
枚とを積層して極板群を作った。そして２０ kg/cm2 の
圧力で極板群を積層方向に加圧する電槽内に極板群を配
置し、さらに電槽内に規定量の電解液を注液して密閉形
鉛蓄電池を完成した。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment in which the present invention is applied to a sealed lead-acid battery will be described below in detail with reference to the drawings. The sealed lead-acid battery of this example was manufactured as follows. First, Si
(OC 2 H 5) 4 was gradually added a proportion of 1 wt% sulfuric acid for Si (OC 2 H 5) 4 to the solution with stirring an aqueous solution containing 20 wt%, the viscosity of the solution is equal to or greater than 10poise By the way, a silica gel fiber having an average wire diameter of 4 μm was produced by a sol-gel method in which this solution was pulled through a nozzle. Next, 2% by weight of this silica gel fiber with a length of 2 mm
And 50% by weight of SiO 2 powder having an average particle size of 10 to 30 nm
And 20% by weight of an inorganic powder composed of 50% by weight of diatomaceous earth having an average particle size of 5 to 70 μm, and a wire diameter of 0.2 mm having a length of 2 mm.
A 7 μm glass fiber and 0.5% by weight of an inorganic powder adsorbent made of polyamide acrylamide were dispersed in pure water to form a paper, dried, and dried to obtain a 2.4 mm-thick non-woven electrolyte holder. Had made. It is preferable that the electrolyte solution holder has a weight specific surface area of 20 to 80 m 2 / g as a whole. The preferable addition amount of the silica gel fiber to the whole electrolyte holder is 2 to 3% by weight, and the preferable addition amount of the inorganic powder to the whole electrolyte holder is 20 to 80% by weight. Next, with the electrolyte holder interposed therebetween, eight paste type positive electrode plates (240 mm high × 140 mm width) and a known paste type negative electrode plate (240 mm high × 140 mm width) 9
The electrodes were stacked to form an electrode group. The electrode group is placed in a battery case that presses the electrode group in the stacking direction with a pressure of 20 kg / cm 2 , and a specified amount of electrolyte is injected into the battery case to complete a sealed lead-acid battery. did.
【００１０】次に本実施例の密閉形蓄電池の特性を調べ
るために、電池ａ〜ｊを各３個づつ作り、試験を行っ
た。電池ａは本実施例の密閉形蓄電池であり、電池ｂ〜
ｄは無機物粉体及びシリカゲル繊維の含有量がそれぞれ
好ましい範囲で異なる実施例の密閉形蓄電池であり、電
池ｅ〜ｈは電解液保持体に対する無機物粉体及びシリカ
ゲル繊維の含有量がそれぞれ異なる本発明の他の実施例
の電池であり、電池ｉは電解液保持体にシリカゲル繊維
を含有させない従来の電池であり、電池ｊは電解液保持
体に無機物粉体及びシリカゲル繊維を含有させない従来
の電池である。尚、各電池の無機物粉体及びシリカゲル
繊維の含有量は表１に示す通りである。Next, in order to examine the characteristics of the sealed storage battery of this embodiment, three batteries a to j were prepared and tested. Battery a is the sealed storage battery of the present embodiment, and batteries b to
d is a sealed storage battery of an embodiment in which the content of the inorganic powder and the content of the silica gel fiber are different within a preferable range, and the batteries e to h have different contents of the inorganic powder and the silica gel fiber with respect to the electrolyte holder, respectively. In another embodiment, the battery i is a conventional battery that does not contain silica gel fibers in the electrolyte holder, and the battery j is a conventional battery that does not contain inorganic powder and silica gel fibers in the electrolyte holder. is there. The contents of the inorganic powder and the silica gel fiber in each battery are as shown in Table 1.
【００１１】[0011]
【表１】 そして各電池ａ〜ｊを、周囲温度２５℃において０．１
ＣＡ（終止電圧１．８Ｖ／セル）で放電した後に２．３
０Ｖ／セル（制限電流０．１ＣＡ）で４８時間定電圧充
電する充放電を繰り返し、各電池のサイクル寿命特性を
調べた。図１はその測定結果を示している。本図より本
実施例の電池ａ及び無機物粉体及びシリカゲル繊維の含
有量が好ましい範囲の電池ｂ〜ｄのサイクル寿命特性が
高いのが判る。[Table 1] Then, each of the batteries a to j is set to 0.1 at an ambient temperature of 25 ° C.
2.3 after discharging at CA (final voltage 1.8 V / cell)
The charge / discharge with constant voltage charging at 0 V / cell (limited current 0.1 CA) for 48 hours was repeated, and the cycle life characteristics of each battery were examined. FIG. 1 shows the measurement results. From this figure, it can be seen that the cycle life characteristics of the battery a of this example and the batteries b to d in which the contents of the inorganic powder and the silica gel fiber are in the preferable ranges are high.
【００１２】また前述の充放電試験において３０サイク
ル目の充放電を終えた電池ａ〜ｊを解体して電解液保持
体の上部と下部との電解液比重の差を測定したところ、
他の実施例の電池ｅ〜ｈでは比重差の平均値が０．０５
〜０．０９、従来の電池ｉ，ｊでは比重差の平均値が
０．１８〜０．２０であったのに対して本実施例の電池
ａ及び無機物粉体及びシリカゲル繊維の含有量が好まし
い範囲の電池ｂ〜ｄでは比重差の平均値が０．００３〜
０．００６であった。これより無機物粉体及びシリカゲ
ル繊維の含有量を好ましい範囲にすると電池に充放電を
繰り返しても電解液が成層化しにくいのが判る。In the above-mentioned charge / discharge test, the batteries a to j which had been charged / discharged in the 30th cycle were disassembled and the difference in the specific gravity of the electrolyte between the upper and lower portions of the electrolyte holder was measured.
In the batteries e to h of other examples, the average value of the specific gravity difference was 0.05.
While the average value of the specific gravity difference was 0.18 to 0.20 in the conventional batteries i and j, the content of the battery a and the inorganic powder and the silica gel fiber in the present example were preferable. In the range of batteries b to d, the average value of the specific gravity difference is 0.003 to
It was 0.006. From this, it can be seen that when the contents of the inorganic powder and the silica gel fiber are in the preferable ranges, the electrolyte is hardly stratified even if the battery is repeatedly charged and discharged.
【００１３】[0013]
【発明の効果】請求項１の発明によれば、電解液保持体
にシリカゲル繊維を含有させるので、シリカゲル繊維の
一部が電解液中に溶解して電解液保持体がほぐれる。そ
の結果、電解液保持体と極板との間の密着性が高まり、
極板と電解液保持体との界面における電解液の成層化を
抑制して、電池の容量を高め、寿命を延ばすことができ
る。また本発明によれば、シリカゲル繊維の一部が電解
液中に溶解して電解液の粘性が高くなることによっても
電解液の成層化を抑制することができる。According to the first aspect of the present invention, since the silica gel fibers are contained in the electrolyte holder, a part of the silica gel fibers is dissolved in the electrolyte and the electrolyte holder is loosened. As a result, the adhesion between the electrolyte holder and the electrode plate is increased,
It is possible to suppress the stratification of the electrolyte at the interface between the electrode plate and the electrolyte holder, increase the capacity of the battery, and extend the life. Further, according to the present invention, stratification of the electrolytic solution can be suppressed by dissolving part of the silica gel fibers in the electrolytic solution and increasing the viscosity of the electrolytic solution.
【００１４】請求項２の発明によれば、極板と電解液保
持体との界面部における電解液の成層化を有効に防止す
ることができる。According to the second aspect of the present invention, stratification of the electrolyte at the interface between the electrode plate and the electrolyte holder can be effectively prevented.
【図１】 試験に用いた電池の充放電特性を示す図であ
る。FIG. 1 is a diagram showing charge / discharge characteristics of a battery used in a test.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 10/06 - 10/10 H01M 2/16──────────────────────────────────────────────────の Continued on front page (58) Field surveyed (Int.Cl. 6 , DB name) H01M 10/06-10/10 H01M 2/16
Claims (2)
電解液保持体を間に介在させてペースト式極板を積層し
てなる極板群を有する密閉形蓄電池であって、 前記電解液保持体はシリカゲル繊維を含有していること
を特徴とする密閉形蓄電池。1. A sealed storage battery having an electrode group formed by stacking paste electrode plates with an electrolyte holder containing an inorganic powder holding an electrolyte interposed therebetween, wherein the electrolyte is A sealed storage battery, wherein the holder contains silica gel fibers.
する重量比を２０〜８０％とし、前記シリカゲル繊維の
前記電解液保持体に対する重量比を２〜３％としたこと
を特徴とする請求項１に記載の密閉形蓄電池。2. The weight ratio of the inorganic powder to the electrolyte holder is 20 to 80%, and the weight ratio of the silica gel fibers to the electrolyte holder is 2 to 3%. Item 7. A sealed storage battery according to Item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5030005A JP2768197B2 (en) | 1993-02-19 | 1993-02-19 | Sealed storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5030005A JP2768197B2 (en) | 1993-02-19 | 1993-02-19 | Sealed storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06243888A JPH06243888A (en) | 1994-09-02 |
| JP2768197B2 true JP2768197B2 (en) | 1998-06-25 |
Family
ID=12291781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5030005A Expired - Fee Related JP2768197B2 (en) | 1993-02-19 | 1993-02-19 | Sealed storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2768197B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016177872A (en) * | 2015-03-18 | 2016-10-06 | 日立化成株式会社 | Lead storage battery |
-
1993
- 1993-02-19 JP JP5030005A patent/JP2768197B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06243888A (en) | 1994-09-02 |
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