JPH01253154A - Sealed lead-acid battery - Google Patents
Sealed lead-acid batteryInfo
- Publication number
- JPH01253154A JPH01253154A JP63079582A JP7958288A JPH01253154A JP H01253154 A JPH01253154 A JP H01253154A JP 63079582 A JP63079582 A JP 63079582A JP 7958288 A JP7958288 A JP 7958288A JP H01253154 A JPH01253154 A JP H01253154A
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- acid
- glass fibers
- sealed lead
- 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
- 239000003792 electrolyte Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000003365 glass fiber Substances 0.000 claims abstract description 17
- 238000013517 stratification Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 230000000670 limiting effect Effects 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012209 synthetic fiber Substances 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011800 void material Substances 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
- H01M10/10—Immobilising of electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
- H01M50/437—Glass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
- Secondary Cells (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
負極吸収式の密閉形鉛蓄電池は、電解液の希硫酸を実質
的に非流動化し、充電時に正極から発生する酸素ガスを
負極活物質で吸収することを特徴とする電池である。そ
して電池外部へのガス排出がほとんどなく、補水等の保
守が不易テ
要となり、メインナナンスフリーであり、液もれしない
ことによるポジションフリーに加え、さらにコンパクト
タイプである。このためＯＡ機器のバックアップ電源と
して急速に拡大し、従来の液式鉛蓄電池に比べて安全性
や信頼性を大幅に向上したものである。BACKGROUND ART A negative electrode absorption type sealed lead acid battery is a battery characterized by making the dilute sulfuric acid of the electrolyte substantially non-fluidized and absorbing the oxygen gas generated from the positive electrode during charging by the negative electrode active material. In addition, there is almost no gas discharge to the outside of the battery, maintenance such as water replenishment is not required, there is no main maintenance, and there is no positioning due to no leakage, and it is also a compact type. For this reason, they have rapidly expanded as a backup power source for office automation equipment, and have significantly improved safety and reliability compared to conventional liquid lead-acid batteries.
この密閉形鉛蓄電池に使用される電解液保持体及び隔離
体は、正極と負極との電導性を確保し、電池容量に必要
な硫酸を保持すると共に充放電の際に両極との間に硫酸
の供給、吸収をスムーズに行なう特性を備えていること
が必要である。さらに充電中暢正極で発生する酸素が負
極まで移動可能な空間を保有していること、そして負極
板上での吸収反応が十分に行われることが必要である。The electrolyte holder and separator used in this sealed lead-acid battery ensure conductivity between the positive and negative electrodes, retain the sulfuric acid necessary for battery capacity, and maintain the sulfuric acid between the two electrodes during charging and discharging. It is necessary to have characteristics that allow for smooth supply and absorption of water. Furthermore, it is necessary that there is a space in which oxygen generated at the positive electrode can move to the negative electrode during charging, and that the absorption reaction on the negative electrode plate is sufficiently carried out.
現在、これらの機能を持つ密閉形鉛蓄電池とするため、
一般に次の電解液保持方法をとっている。Currently, in order to make a sealed lead-acid battery with these functions,
Generally, the following electrolyte retention method is used.
（１）ガラス繊維等を混抄して不織布とし、これに電解
液を吸収、保持させる方法（以下「リテーナ式」と称す
）。(1) A method in which a nonwoven fabric is made by mixing glass fiber or the like, and the electrolyte is absorbed and retained in this fabric (hereinafter referred to as the "retainer type").
（２） シリカ等の無機酸化物よりなるゲル状物で電
解液を保持させる方法（以下「ゲル式」と称す）。(2) A method in which the electrolyte is held in a gel-like material made of an inorganic oxide such as silica (hereinafter referred to as "gel method").
（３）耐酸性の無機粉体をガラス繊維や合成繊維に含有
させる方法（以下「粉体式」と称す）リテーナ式の電解
液保持体は微細なガラス繊維、合成繊維そしてバインダ
ーなどの混抄された不織布である。電解液保持体の構成
は、例えば７０〜８０ Ｖｏ１％の電解液、５〜１０Ｖ
ｏ１％のガラス繊維そして１５〜２０ Ｖｏ１％の空間
から成っている。従って、液の移動も容易であり電池特
性も良く、かつ負極での酸素ガス吸収も十分におこなわ
れており、現在の負極吸収式鉛蓄電池の多くがこのリテ
ーナ式となっている。(3) Method of incorporating acid-resistant inorganic powder into glass fibers or synthetic fibers (hereinafter referred to as "powder method") The retainer-type electrolyte holder is a mixture of fine glass fibers, synthetic fibers, binders, etc. It is a non-woven fabric. The structure of the electrolyte holder is, for example, 70-80 Vo1% electrolyte, 5-10V
It consists of 1% glass fiber and 15-20 1% void. Therefore, liquid movement is easy, battery characteristics are good, and oxygen gas absorption at the negative electrode is sufficiently performed, and many of the current negative electrode absorption type lead-acid batteries are of this retainer type.
一方、ゲル式では、シリカ粒子を希硫酸と混合してゲル
化させているため、酸素ガスの移動と負極でのガス吸収
を阻害しがちであり、さらに振動によるゾル化によって
極板からゲルが離れてしまうなど電池特性に悪影響を与
えがちである。また製造する工程が複雑となりコストア
ップにつながる。On the other hand, in the gel type, silica particles are mixed with dilute sulfuric acid to form a gel, which tends to inhibit the movement of oxygen gas and gas absorption at the negative electrode, and furthermore, the gel is removed from the electrode plate due to sol formation due to vibration. This tends to have an adverse effect on battery characteristics, such as causing them to become separated from each other. Furthermore, the manufacturing process becomes complicated, leading to increased costs.
ところで、リテーナ式の密閉形鉛蓄電池においては、特
に大容量仕様では極板が大きくなり、充電・放電によっ
て電池の上部の電解液濃度が低くそして底部の電解液濃
度が高くなる、いわゆる成層化現象が生じる。この解消
はむづかしく、電池性能を低下させ、短寿命とする大き
な原因となっている。このためゲル式の大容量電池が考
えられているが、上記のごとく特性上と製造上の問題の
ため、高性能な電池になっていない。By the way, in cage-type sealed lead-acid batteries, especially in high-capacity specifications, the electrode plates become large, and due to charging and discharging, the electrolyte concentration at the top of the battery becomes low and the electrolyte concentration at the bottom becomes high, which is a so-called stratification phenomenon. occurs. This problem is difficult to resolve and is a major cause of deterioration in battery performance and shortened lifespan. For this reason, gel-type large-capacity batteries have been considered, but due to the characteristics and manufacturing problems described above, high-performance batteries have not been achieved.
これに対して、粉体式の電解液保持体は電解液の成層化
を抑制でき、そして密閉形鉛蓄電池として十分な特性を
示す電池になることが判っており、種々使用される条件
に合致する密閉形鉛蓄電池として、急速に研究が進み製
品化への展開がなされている。On the other hand, it has been found that the powder-type electrolyte holder can suppress stratification of the electrolyte and exhibit sufficient characteristics as a sealed lead-acid battery, meeting various usage conditions. As a sealed lead-acid battery, research is progressing rapidly and it is being commercialized.
発明が解決しようとする課題
無機粉体と種々繊維を主体とする電解液保持体では、成
層化を防止するため各々の含有量子種類を検討し、電池
に適した仕様を決めている。Problems to be Solved by the Invention In order to prevent stratification in electrolyte holders mainly composed of inorganic powder and various fibers, the types of quantum contained in each are studied to determine specifications suitable for batteries.
従来はリテーナ式の電解液保持体が高価であったため、
無機粉体を含有させることでコストダウンを主眼に置い
て検討されていた。さらにガラス繊維を太くすることで
、コストダウンをねらっていた。Previously, retainer-type electrolyte holders were expensive;
Studies have focused on cost reduction by including inorganic powder. They also aimed to reduce costs by making the glass fiber thicker.
ところが、取扱い上の問題として、電解液保持体の割れ
や粉体の脱落が起こり、その対策としてフィブリル状の
合成繊維の添加や合成繊維自体の増加が行われてきた。However, handling problems include cracking of the electrolyte holder and falling of the powder, and as a countermeasure to this problem, fibrillar synthetic fibers have been added or synthetic fibers themselves have been increased.
このことはコストアップと硫酸と新和性の低い素材の増
加による曵
電池性能の低下となって行われてきている。This has resulted in increased costs and decreased battery performance due to increased use of sulfuric acid and less compatible materials.
また粉体量をさらに多くすることで、コストダウンをお
こなっているが、電解液保持体自体が硬くなりまた粉体
も脱落すること、そして保持体内部の粉体が大きな塊と
して存在するようになり、電解液の保持と供給が低下す
ること等の問題が起こった。In addition, by increasing the amount of powder, costs are reduced, but the electrolyte holder itself becomes hard and the powder falls off, and the powder inside the holder tends to exist as large lumps. This caused problems such as a decrease in electrolyte retention and supply.
このように種々問題を解決して安い電解液保持体を作ろ
うとしているが、組成が複雑になり予想された効果が表
われにくく、逆に製造仕様の複雑化によりコストアップ
さえなっている。Attempts have been made to solve these various problems in order to produce an inexpensive electrolyte holder, but the composition has become complicated, making it difficult to achieve the expected effects, and conversely, the complexity of manufacturing specifications has even increased costs.
課題を解決するための手段
本発明は上記の課題を解決するためになされたもので、
平均直径が１．０μｍ未満のガラス繊維に、耐酸性の無
機粉体を４０〜７０重量％含有した多孔体を電解液保持
体として使用したことを特徴とするものである。Means for Solving the Problems The present invention has been made to solve the above problems.
It is characterized in that a porous body containing 40 to 70% by weight of acid-resistant inorganic powder in glass fibers having an average diameter of less than 1.0 μm is used as an electrolyte holder.
作用
本発明は上記の特徴を有することにより、ガ還
ラス繊維の種類を平均直径１．０μｍ末端に限定するこ
とで単純化し、かつ４０〜７０重量％と多量の無機粉体
を使用することで、材料の面さらに製造上よりコストダ
ウンすると共に、電解液の成層化問題を改善できる電解
液保持体を備えた密閉形鉛蓄電池を提供するものである
。Operation The present invention has the above-mentioned characteristics, and is simplified by limiting the type of glass-reduced glass fibers to those with an average diameter of 1.0 μm at the ends, and by using a large amount of inorganic powder of 40 to 70% by weight. It is an object of the present invention to provide a sealed lead-acid battery equipped with an electrolyte holder that can reduce costs in terms of materials and manufacturing, and improve the problem of stratification of the electrolyte.
実施例 本発明の一実施例を説明する。Example An embodiment of the present invention will be described.
第１表の電解液保持体の組成のように、ガラス繊維とし
て平均直径０．７μｍ、４μｍ、１６μｍ、無機粉体と
して珪酸粉体と珪藻土を原料として、純水にて撹拌混合
し、抄造後乾燥して厚さ２．４ｍｉの多孔体からなる電
解液保持体を作成した。As shown in the composition of the electrolyte holder in Table 1, glass fibers with average diameters of 0.7 μm, 4 μm, and 16 μm, and inorganic powders of silicic acid powder and diatomaceous earth are used as raw materials, stirred and mixed with pure water, and after papermaking. After drying, an electrolyte holder made of a porous material having a thickness of 2.4 mm was prepared.
また、これらの電解液保持体と高さ２５０ｍｍ極板とを
用いて２００Ａｈ密閉形鉛蓄電池を製作した。比重１
、３００の電解液を注入し、電池容量を確認した後、「
放電４０Ａ （０，２ＣＡ）、８時間；充電６０Ａ （
０，３ＣＡ）、充電電圧２．４５Ｖ／セル、８時間；温
度２０°ＣＪの条件でサイクル試験した。そしで１０サ
イクル後に解体し、電池の極板上部と下部の比重を測定
し、その比重差を測定した。Furthermore, a 200 Ah sealed lead acid battery was manufactured using these electrolyte holders and electrode plates with a height of 250 mm. Specific gravity 1
, after injecting 300 ml of electrolyte and checking the battery capacity,
Discharge 40A (0.2CA), 8 hours; Charge 60A (
0.3 CA), charging voltage 2.45 V/cell, 8 hours; temperature 20°CJ. After 10 cycles, the battery was disassembled, the specific gravity of the upper and lower electrode plates of the battery was measured, and the difference in specific gravity was measured.
第１表で示した結果により、平均直径が１．０μｍ未満
のガラス繊維の場合、無機粉体量が４０〜７０重量％の
時に電解液の成層化が抑制されている。−船釣に成層化
として問題になるのは、比重差が０．０５以上め時であ
り、０．０３から０．０５の間は注意するレベルと考え
ている。According to the results shown in Table 1, in the case of glass fibers having an average diameter of less than 1.0 μm, stratification of the electrolytic solution is suppressed when the amount of inorganic powder is 40 to 70% by weight. - Stratification becomes a problem in boat fishing when the difference in specific gravity is 0.05 or more, and I believe that anything between 0.03 and 0.05 is a level to be careful about.
ガラス繊維の太さについては、例えば平均直径４．０μ
ｍを混抄すると、比重差がおおきくなり電池の機種によ
っては注意すべきレベルとなる。また１、０１１ｍ未満
のガラス繊維が含まれない場合は、明らかに比重差が大
きくなる。このように、平均直径１．０μｍ以上のガラ
ス繊維を含むと、成層化を大きくすることが判った。Regarding the thickness of glass fiber, for example, the average diameter is 4.0μ
If M is mixed, the difference in specific gravity will become large, and depending on the type of battery, it will be at a level that requires caution. Moreover, when glass fibers of less than 1,011 m are not included, the difference in specific gravity becomes clearly large. Thus, it has been found that inclusion of glass fibers with an average diameter of 1.0 μm or more increases stratification.
発明の効果
上述したように、本発明によれば、平均直径が１．０μ
ｍ未満のガラス繊維に耐酸性の無機粉体を４０〜７０重
量％含有した多孔体を電解液保持体として用いたため、
密閉形鉛蓄電池の電解液成層化を抑制できると共に、無
機粉体を多く使うことによるコストダウンが可能となる
効果がある。Effects of the Invention As described above, according to the present invention, the average diameter is 1.0μ.
Since a porous body containing 40 to 70% by weight of acid-resistant inorganic powder in glass fibers of less than m was used as an electrolyte holder,
This has the effect of suppressing electrolyte stratification in sealed lead-acid batteries and reducing costs by using a large amount of inorganic powder.
Claims (1)
機粉体を４０〜７０重量パーセント含有してなる多孔体
を電解液保持体として用いたことを特徴とする密閉形鉛
蓄電池。A sealed lead-acid battery characterized in that a porous body made of glass fibers having an average diameter of less than 1.0 μm and containing 40 to 70 weight percent of acid-resistant inorganic powder is used as an electrolyte holder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63079582A JP2918204B2 (en) | 1988-03-31 | 1988-03-31 | Sealed lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63079582A JP2918204B2 (en) | 1988-03-31 | 1988-03-31 | Sealed lead-acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01253154A true JPH01253154A (en) | 1989-10-09 |
| JP2918204B2 JP2918204B2 (en) | 1999-07-12 |
Family
ID=13693979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63079582A Expired - Lifetime JP2918204B2 (en) | 1988-03-31 | 1988-03-31 | Sealed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2918204B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017224483A (en) * | 2016-06-15 | 2017-12-21 | 日立化成株式会社 | Lead storage battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60221954A (en) * | 1984-04-09 | 1985-11-06 | Nippon Sheet Glass Co Ltd | Separator for storage battery |
| JPS6180750A (en) * | 1984-09-28 | 1986-04-24 | Nippon Muki Kk | Separator for sealed type lead storage battery |
-
1988
- 1988-03-31 JP JP63079582A patent/JP2918204B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60221954A (en) * | 1984-04-09 | 1985-11-06 | Nippon Sheet Glass Co Ltd | Separator for storage battery |
| JPS6180750A (en) * | 1984-09-28 | 1986-04-24 | Nippon Muki Kk | Separator for sealed type lead storage battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017224483A (en) * | 2016-06-15 | 2017-12-21 | 日立化成株式会社 | Lead storage battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2918204B2 (en) | 1999-07-12 |
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