JPH0413829B2 - - Google Patents
Info
- Publication number
- JPH0413829B2 JPH0413829B2 JP60061419A JP6141985A JPH0413829B2 JP H0413829 B2 JPH0413829 B2 JP H0413829B2 JP 60061419 A JP60061419 A JP 60061419A JP 6141985 A JP6141985 A JP 6141985A JP H0413829 B2 JPH0413829 B2 JP H0413829B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode plate
- lead
- positive electrode
- antimony
- lead alloy
- 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 - Lifetime
Links
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 229910052787 antimony Inorganic materials 0.000 claims description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 6
- 239000011245 gel electrolyte Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 239000011149 active material Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 3
- 235000011613 Pinus brutia Nutrition 0.000 description 3
- 241000018646 Pinus brutia Species 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000796 S alloy Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002142 lead-calcium alloy Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005373 porous glass 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
- H01M10/34—Gastight accumulators
- H01M10/342—Gastight lead accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
- H01M4/685—Lead alloys
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Gas Exhaust Devices For Batteries (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Cell Separators (AREA)
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、特にクラツド
式無保守鉛蓄電池に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to improvements in sealed lead-acid batteries, and more particularly to closed-type non-maintenance lead-acid batteries.
従来の技術とその問題点
従来の液式鉛蓄電池は使用する正極板の種類に
よつてペースト式とクラツド式の２種類があり、
高エネルギー密度や高出力が要求される用途には
ペースト式、長寿命が要求される用途にはクラツ
ド式というように使い分けられている。しかし、
密閉形鉛蓄電池は、正極板にペースト式極板を使
用し、電解液を制限して流動性電解液をなくした
構成、いわゆるリテーナペースト式電池に限られ
ている。このようなリテーナペースト式電池の正
極格子には、実質的にアンチモンを含まない鉛合
金、例えば鉛−カルシウム系合金を用いる方法が
最も一般的である。しかし、アンチモンを含まな
い鉛合金に共通した欠点として、結晶粒間が選択
的に腐食しやすく、また伸びが大きく、活物質の
軟化脱落のため、充放電サイクル寿命が短いとい
う問題点があつた。Conventional technology and its problems There are two types of conventional liquid lead-acid batteries, paste type and clad type, depending on the type of positive electrode plate used.
The paste type is used for applications that require high energy density and high output, and the clad type is used for applications that require long life. but,
Sealed lead-acid batteries are limited to so-called retainer paste batteries, which use a paste-type electrode plate for the positive electrode plate, limit the electrolyte, and eliminate the fluid electrolyte. The most common method is to use a lead alloy that does not substantially contain antimony, such as a lead-calcium alloy, for the positive electrode grid of such a retainer paste type battery. However, the common drawbacks of lead alloys that do not contain antimony are that they tend to selectively corrode between crystal grains, are highly elongated, and have a short charge-discharge cycle life due to the active material softening and falling off. .
問題点を解決するための手段
本発明は実質的にアンチモンを含まない鉛合金
芯金を用いたクラツド式正極板と、実質的にアン
チモンを含まない鉛合金格子を用いた負極板とを
耐酸性繊維からなる多孔度の高いマツトを介して
積層して極板群とするとともに、蓋には固定した
排気弁を有し電解液をゲル状とすることを特徴と
するものである。Means for Solving the Problems The present invention provides a clad positive electrode plate using a lead alloy core metal substantially free of antimony, and a negative electrode plate using a lead alloy lattice substantially free of antimony. It is characterized in that it is laminated with a highly porous mat made of fibers interposed therebetween to form a group of electrode plates, has an exhaust valve fixed to the lid, and uses a gel-like electrolyte.
作 用
本発明になる鉛蓄電池では、アンチモンの汚染
による負極板の水素過電圧の低下がなく、自己放
電が少ない。また、正極板としてクラツド式極板
を用いるので、芯金は活物質に囲まれチユーブで
緊密に保持されている。したがつて充放電をされ
ても芯金は二酸化鉛の活物質層で圧迫、保護され
ているので腐食が抑制され伸びが少ないばかりで
なく、活物質層はチユーブと芯金の間〓に緊密に
充填された状態であつて強く保持されているの
で、軟化脱落が少なく、性能低下がなく長寿命で
ある。また、電解液はゲル状であつて漏液の心配
がないばかりでなく、酸素サイクルの密閉反応の
ために減液が少ない。さらに正、負極板間には多
孔度の高いマツトが介在してゲル状電解液を保持
しているので、活物質の脱落および短絡防止機能
を有するのみでなく、正極板には低抵抗の薄いチ
ユーブを用いることができ、放電性能が高められ
る。なお、電解液をゲル状とした通常のペースト
式密閉形鉛蓄電池においては、活物質の脱落、短
絡を防ぐために孔の小さな緻密な組織を有し多孔
度が高くない微孔板、すなわち平均孔径10μ以
下、多孔度40〜60％の微孔板をセパレータとして
用いる必要があるが、クラツド式正極板を用いた
場合にはチユーブが活物質の脱落を防ぐので多孔
度の高いマツトをセパレータとして用いることが
可能となる。また芯金の伸びによりチユーブ両端
が連座からはずれるようなことがあつても活物質
脱落のおそれが少ない。Effects In the lead-acid battery according to the present invention, there is no drop in the hydrogen overvoltage of the negative electrode plate due to antimony contamination, and there is little self-discharge. Furthermore, since a clad plate is used as the positive electrode plate, the core metal is surrounded by the active material and tightly held by the tube. Therefore, even when charging and discharging, the core metal is compressed and protected by the active material layer of lead dioxide, which not only suppresses corrosion and reduces elongation, but also keeps the active material layer tightly between the tube and the core metal. Since it is strongly held in the filled state, there is little softening and falling off, and there is no performance deterioration, resulting in a long life. Furthermore, since the electrolyte is in a gel form, there is no risk of leakage, and there is little loss of liquid due to the sealed reaction of the oxygen cycle. Furthermore, since a highly porous mat is interposed between the positive and negative electrode plates to hold the gel electrolyte, it not only has the function of preventing active material from falling off and short circuits, but also has a low-resistance thin layer on the positive electrode plate. A tube can be used to improve discharge performance. In addition, in normal paste-type sealed lead-acid batteries with a gel electrolyte, a microporous plate with a dense structure with small pores and a low porosity is used to prevent the active material from falling off and short circuiting. It is necessary to use a microporous plate of 10 μ or less and a porosity of 40 to 60% as a separator, but when using a clad positive electrode plate, the tube prevents the active material from falling off, so a highly porous pine plate is used as the separator. becomes possible. Furthermore, even if both ends of the tube become detached from the joint due to elongation of the core metal, there is little risk of the active material falling off.
実施例
本発明になる鉛蓄電池の一実施例を第１図に示
す。図において、１は実質的にアンチモンを含ま
ない鉛合金、例えば鉛−カルシウム−すず−アル
ミニウム合金、アンチモン１％以下の鉛−アンチ
モン−ひ素−すず−硫黄合金などからなる芯金、
２はチユーブ、３は正極活物質、４は上部鉛合金
連座、５は下部連座であり、これら１〜５でクラ
ツド式正極板を構成する。６は実質的にアンチモ
ンを含まない鉛合金、例えば鉛−カルシウム−ア
ルミニウム合金からなる格子を用いた負極板、７
は多孔度の高いマツトで耐酸性繊維例えば含アル
カリガラス、アクリル、ポリエステル、ポリエチ
レンとからなる直径30μ以下の細い繊維を用いる
マツトであり、鉛蓄電池で常用されている直径約
20μの長繊維からなるガラスツト、直径約10μの
短繊維を抄紙したガラスマツトおよび直径0.5〜
5μの短繊維を抄紙した極細ガラスマツトを用い
ることができる。多孔度は70％以上、好ましくは
90％から97％、平均孔径は10μ以上である。この
マツトは正極板および負極板の間に配置されてゲ
ル状電解液を保持するとともに、セパレータの機
能を持つものである。そのために厚さは0.5mm〜
５mm、特に1.0〜2.0のものが好ましい。８は電槽
および蓋、９はゲル状電解液でシリカの微粒子と
希硫酸酸とからなり、マツト内の多孔部およびク
ラツド式正極板の周囲などの極板群内の空所なら
びに極板群の周囲の空所に充填されている。すな
わち、正極板は芯金１、チユーブ２、正極活物質
３、上部鉛合金連座４および下部鉛合金連座５で
構成され、この正極板と負極板６およびマツト７
からなる極板群は、ゲル状電解液９に埋没させて
配置されている。シリカの濃度は３〜20重量％が
使用できるが、特に５〜10重量％のものが放電容
量ならびに寿命性能で優れていて好ましい。１０
は蓋の一部に固定されている排気弁、１１は正極
端子、１２は負極端子である。本発明になる電池
はセパレータとして多孔度の高いガラスマツトを
用いているので放電容量が大きく良好である。ま
た、正極板としてクラツド式極板を用いているの
で充放電サイクル寿命性能も優れている。Embodiment FIG. 1 shows an embodiment of a lead-acid battery according to the present invention. In the figure, 1 is a core made of a lead alloy that does not substantially contain antimony, such as a lead-calcium-tin-aluminum alloy, a lead-antimony-arsenic-tin-sulfur alloy containing 1% or less of antimony;
2 is a tube, 3 is a positive electrode active material, 4 is an upper lead alloy connecting seat, and 5 is a lower connecting seat, and these 1 to 5 constitute a clad type positive electrode plate. 6 is a negative electrode plate using a lattice made of a lead alloy substantially free of antimony, such as a lead-calcium-aluminum alloy; 7
is a highly porous pine made of acid-resistant fibers such as alkali-containing glass, acrylic, polyester, and polyethylene, with a diameter of 30μ or less.
Glass mats made of long fibers of 20μ, glass mats made from short fibers with a diameter of about 10μ, and glass mats with a diameter of 0.5~
An ultra-fine glass mat made of 5μ short fibers can be used. Porosity is 70% or more, preferably
90% to 97%, the average pore size is more than 10μ. This mat is placed between the positive electrode plate and the negative electrode plate to hold the gel electrolyte and also functions as a separator. Therefore, the thickness is 0.5mm~
5 mm, particularly preferably 1.0 to 2.0. 8 is a battery case and a lid; 9 is a gel electrolytic solution made of fine silica particles and dilute sulfuric acid, and is used in porous areas in the mat and in voids in the electrode plate group such as around the clad positive electrode plate, and in the electrode plate group. The void around the is filled in. That is, the positive electrode plate is composed of a core metal 1, a tube 2, a positive electrode active material 3, an upper lead alloy joint seat 4, and a lower lead alloy joint seat 5, and this positive electrode plate, a negative electrode plate 6, and a mat 7
The electrode plate group consisting of the following is disposed so as to be buried in the gel electrolyte 9. A silica concentration of 3 to 20% by weight can be used, but a silica concentration of 5 to 10% by weight is particularly preferred since it is excellent in discharge capacity and life performance. 10
1 is an exhaust valve fixed to a part of the lid, 11 is a positive terminal, and 12 is a negative terminal. Since the battery of the present invention uses a highly porous glass mat as a separator, its discharge capacity is large and good. Furthermore, since a clad type electrode plate is used as the positive electrode plate, the charge/discharge cycle life performance is also excellent.
発明の効果
本発明によれば放電性能に優れた充放電サイク
ル寿命の長いクラツド式の密閉形鉛蓄電池を提供
することができる。Effects of the Invention According to the present invention, it is possible to provide a closed lead-acid battery of a clad type with excellent discharge performance and a long charge/discharge cycle life.
第１図は本発明になるクラツド式無保守鉛蓄電
池を示す要部縦断面模式図である。
１……実質的にアンチモンを含まない鉛合金か
らなる芯金、２……チユーブ、３……正極活物
質、６……実質的にアンチモンを含まない鉛合金
格子を用いた負極板、７……多孔度の高いマツ
ト、９……ゲル状電解液、１０……排気弁。
FIG. 1 is a schematic vertical cross-sectional view of the essential parts of a clad type non-maintenance lead-acid battery according to the present invention. DESCRIPTION OF SYMBOLS 1...A core made of a lead alloy that does not substantially contain antimony, 2...A tube, 3...A positive electrode active material, 6...A negative electrode plate that uses a lead alloy grid that does not substantially contain antimony, 7... ...highly porous pine, 9...gel electrolyte, 10...exhaust valve.
Claims (1)
１、チユーブ２、芯金とチユーブの間に充填され
た正極活物質３、上部鉛合金連座４および下部連
座５で構成されたクラツド式正極板と、実質的に
アンチモンを含まない鉛合金格子を用いた負極板
６とを耐酸性繊維からなる多孔度70％以上のマツ
ト７を介して積層して極板群とするとともに、蓋
には固定した排気弁１０を有し、電解液をゲル状
として該極板群を埋没させて配置したクラツド式
密閉形鉛蓄電池。1 A clad type positive electrode plate consisting of a lead alloy core 1 substantially free of antimony, a tube 2, a positive electrode active material 3 filled between the core and the tube, an upper lead alloy connector 4 and a lower connector 5. A negative electrode plate 6 using a lead alloy lattice that does not substantially contain antimony is laminated via a mat 7 made of acid-resistant fiber with a porosity of 70% or more to form an electrode plate group, and is fixed to the lid. A closed type lead-acid battery having an exhaust valve 10 and having a gel electrolyte and a group of electrode plates buried therein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60061419A JPS61220275A (en) | 1985-03-25 | 1985-03-25 | Nonmaintenance clad lead storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60061419A JPS61220275A (en) | 1985-03-25 | 1985-03-25 | Nonmaintenance clad lead storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61220275A JPS61220275A (en) | 1986-09-30 |
| JPH0413829B2 true JPH0413829B2 (en) | 1992-03-10 |
Family
ID=13170559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60061419A Granted JPS61220275A (en) | 1985-03-25 | 1985-03-25 | Nonmaintenance clad lead storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61220275A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2727793B1 (en) * | 1994-12-01 | 1997-01-17 | Europ Accumulateurs | COMBINATION OF A SEPARATOR AND AN ELECTROLYTE FOR A GAS RECOMBINANT LEAD ACCUMULATOR, AND ACCUMULATOR USING SUCH A COMBINATION |
-
1985
- 1985-03-25 JP JP60061419A patent/JPS61220275A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61220275A (en) | 1986-09-30 |
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