JPH0346768A - Lead storage battery - Google Patents
Lead storage batteryInfo
- Publication number
- JPH0346768A JPH0346768A JP1181054A JP18105489A JPH0346768A JP H0346768 A JPH0346768 A JP H0346768A JP 1181054 A JP1181054 A JP 1181054A JP 18105489 A JP18105489 A JP 18105489A JP H0346768 A JPH0346768 A JP H0346768A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- antimony
- electrolyte
- alloy
- electrode
- 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
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 229910052787 antimony Inorganic materials 0.000 claims description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002142 lead-calcium alloy Substances 0.000 claims description 9
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 7
- 239000000956 alloy Substances 0.000 abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 abstract 2
- 229910017835 Sb—Sn Inorganic materials 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 238000007600 charging Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910001245 Sb 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
- 239000011149 active material Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000002140 antimony alloy Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic 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
-
- 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
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、自動車用、民生機器用、産業用に広く用いら
れている鉛蓄電池に関するもので、自己放電特性、過放
電放置後の充電受入性を改善するものである。[Detailed Description of the Invention] Industrial Application Field The present invention relates to lead-acid batteries that are widely used in automobiles, consumer electronics, and industrial applications. It is something to improve.
従来の技術
今般、自動車用鉛蓄電池は管理不要のメンテナンスフリ
ー化が要求され、電池用格子材料として鉛−カルシウム
系合金が実用化されている、又、近年カーエレクトロニ
クスの著しい発展により電池に関する負荷が増大し、エ
ンジンルームの高密度化により電池が高温状態で使用さ
れ非常に過酷な条件で使用される機会が増えている。メ
ンテナンスフリー性能を維持し高温、高負荷での寿命特
性の改善として、格子表面にアンチモンを多く有する層
を形成させるなどの手段が使われている。Conventional Technology Nowadays, lead-acid batteries for automobiles are required to be maintenance-free, and lead-calcium alloys have been put into practical use as grid materials for batteries.In addition, due to the remarkable development of car electronics in recent years, the load on batteries has increased. Due to the increasing density of engine compartments, batteries are increasingly being used at high temperatures and under extremely harsh conditions. In order to maintain maintenance-free performance and improve life characteristics under high temperatures and high loads, methods such as forming a layer containing a large amount of antimony on the lattice surface are used.
一方、鉛蓄電池は、長期放置または過放電状態で放置さ
れると、充電不能となることが多く、使用不能となる。On the other hand, if a lead-acid battery is left unused for a long period of time or left in an over-discharged state, it often becomes unable to be charged and becomes unusable.
こうした欠点を改善する方法として、従来過放電後の充
電受入れ性能に効果がある、すすを格子合金中に添加あ
るいは、表面にコーティングしたり、電解液中にリン酸
や、アルカリ金属イオンを添加する方法がある。Conventionally, methods to improve these drawbacks include adding soot to the lattice alloy or coating it on the surface, and adding phosphoric acid or alkali metal ions to the electrolyte, which are effective in improving charge acceptance performance after overdischarge. There is a way.
発明が解決しようとした課題
過放電放置後、または長期放置により格子活物質界面に
絶縁層が形成される。このため格子−活物質界面に充電
電流が流れにくくなり、充電不能となる。この欠点を改
善する方法として格子合金中または、表面にすすを添加
する方法があるが、高温、高負荷寿命特性の改善にはほ
とんど効果がない。Problems to be Solved by the Invention An insulating layer is formed at the interface of the lattice active material after over-discharge or long-term storage. This makes it difficult for charging current to flow through the lattice-active material interface, making charging impossible. One way to improve this drawback is to add soot to the lattice alloy or to its surface, but this method has little effect on improving the high-temperature, high-load life characteristics.
又、電解液中へのりん酸添加は、初期容量が低下し、自
己放電は大きくなる。さらに、電解液中へのアルカリ金
属添加は、過放電放置された電解液の電動性を向上させ
る働きがあり、充電特性を向上させる働きがある。Furthermore, when phosphoric acid is added to the electrolyte, the initial capacity decreases and self-discharge increases. Furthermore, the addition of an alkali metal to the electrolytic solution has the function of improving the electrolyte of the electrolytic solution left over-discharged, and has the function of improving the charging characteristics.
しかし、長期放置、過放電放置後に生成する絶縁皮膜に
対しては、あまり効果がない。However, it is not very effective against the insulating film that forms after being left for a long time or over discharged.
本発明は、上記従来の問題点を解決するもので優れたメ
ンテナンスフリー性、高温、深い放電での寿命特性を維
持しつつ、自己放電特性、過放電放置後の充電受入性を
改善するものである。The present invention solves the above-mentioned conventional problems, and improves self-discharge characteristics and charge acceptance after over-discharging while maintaining excellent maintenance-free properties and long-life characteristics at high temperatures and deep discharges. be.
課題を解決するための手段
この目的を達成するために本発明は、アンチモンを含ま
ない鉛−カルシウム系合金の表面にアンチモンを多く含
んだ層を有する電極を用い、かつ電解液中にアルカリ金
属イオンと、アルカリ土類イオンの少なくとも一方を存
在させるものである。Means for Solving the Problems To achieve this object, the present invention uses an electrode having an antimony-rich layer on the surface of a lead-calcium alloy that does not contain antimony, and alkali metal ions in the electrolyte. and alkaline earth ions.
電極表面のアンチモンを多く含んだ層は、鉛−アンチモ
ン、または鉛−アンチモン−すず合金薄膜を、鉛−カル
シウム系合金上に付与させたものである。The antimony-rich layer on the electrode surface is formed by applying a lead-antimony or lead-antimony-tin alloy thin film onto a lead-calcium alloy.
作用
この構成により、優れたメンテナンスフリー性、高温、
深い放電での寿命特性を維持しつつ、自己放電特性、過
放電後の充電受入性を改善することができる。This configuration provides excellent maintenance-free, high-temperature,
It is possible to improve self-discharge characteristics and charge acceptance after overdischarge while maintaining life characteristics under deep discharge.
実施例
以下本発明の一実施例について、図面を参照にしながら
説明する。EXAMPLE An example of the present invention will be described below with reference to the drawings.
鉛−カルシウム合金表面に鉛−５ｗｔ％アンチモン合金
薄膜を付与して格子体としだもの鉛−６ｗｔ％アンチモ
ン−５ｗｔ％すず合金薄膜を付与して格子体としたもの
、比較のために鉛−カルシウム合金を格子体としたもの
を正極格子とし、酸化鉛、硫酸、水を混合したベースと
を充填し、正極板として、負極板とセパレーターをくみ
あわせ、１２Ｖ、６時間率で４８ムｈの電池を作成した
。A lead-calcium alloy surface was coated with a lead-5wt% antimony alloy thin film to form a lattice body.A lead-6wt% antimony-5wt% tin alloy thin film was applied to the lead-calcium alloy surface to form a lattice body.For comparison, a lead-calcium alloy A positive electrode grid is made of an alloy, filled with a base made of a mixture of lead oxide, sulfuric acid, and water, and a negative electrode plate and separator are combined as the positive electrode plate to form a 48 mh battery at 12 V and a 6 hour rate. It was created.
また、アルカリ金属イオンとして、Ｎ ａ＋ 、アル
２＋
カリ土類金属イオンとしてＭｇ イオンを電解液中
に添加した。この電池を９．６ムで６時間定電流放電し
たのち常温で１力月放置した。放置後これらの電池を１
４．８ Ｖ定電圧充電を行いその時の充電電流を測定し
た。Further, Na+ was added as an alkali metal ion, and Mg ion was added as an alkaline earth metal ion to the electrolytic solution. This battery was subjected to constant current discharge at 9.6 μm for 6 hours and then left at room temperature for 1 month. After leaving these batteries 1
4.8 V constant voltage charging was performed and the charging current at that time was measured.
第１図は、９．６ムで６時間定電流放電したのち常温で
１力月放置し、放置後の電池を１４，８ Ｖで定電圧充
電を行いその時の１０秒口重３０秒目。Figure 1 shows a battery that was discharged at a constant current of 9.6 volts for 6 hours, left at room temperature for one month, and then charged at a constant voltage of 14.8 V for 10 seconds at 30 seconds.
６０秒口重電電流値を示したものである、１，２゜３は
鉛−カルシウム合金で、１は電解液に無添加、２は電解
液中に１− を添加したもの、３は電解液中にＭｇ２＋
を添加したものである。４，６゜６は鉛−カルシウム
合金表面に鉛−５ｗｔ％アンチモン合金薄膜を付与して
格子体としたもので、４は電解液に無添加、６は電解液
中にＨａ を添加したもの、６は電解液中にＭ ｇ
２＋ を添加したものである。７，８．９は５ｗｔ％ア
ンチモン−５ｗｔ％すず合金薄膜を付与して格子体とし
たもので、７は電解液に無添加、８は電解液中にＮ ａ
＋を添加したもの、９は電解液中にＭ ｇ ２＋ を添
加したものである。電極表面にアンチモンを付与し、ア
ルカリ金属イオン、アルカリ土類金属イオン添加したも
のの、３０秒口重流は、表面にアンチモンを付与してい
ないものに比較して約２倍、電極表面にアンチモン−す
ずを付与し、アルカリ金属イオン、アルカリ土類金属イ
オン添加したものは、電極表面にアンチモンを付与し、
アルカリ金属イオン、アルカリ土類金属イオン添加した
ものにくらべて３０秒月光電電流は、やや向上した程度
である。1,2゜3 is a lead-calcium alloy, 1 is without addition to the electrolyte, 2 is with 1- added to the electrolyte, and 3 is an electrolyte. Mg2+ in the liquid
is added. 4, 6゜6 has a lead-5wt% antimony alloy thin film applied to the lead-calcium alloy surface to form a lattice, 4 has no addition to the electrolyte, 6 has Ha added to the electrolyte, 6 is Mg in the electrolyte
2+ is added. 7 and 8.9 have a 5wt% antimony-5wt% tin alloy thin film applied to form a lattice body, 7 has no additive in the electrolyte, and 8 has Na in the electrolyte.
9 has M g 2+ added to the electrolytic solution. Although antimony was added to the electrode surface and alkali metal ions and alkaline earth metal ions were added, the 30-second mouth flow was about twice that of the electrode without antimony added to the electrode surface. Those to which tin is added, alkali metal ions, and alkaline earth metal ions are added, antimony is added to the electrode surface,
The 30-second moon photoelectric current was only slightly improved compared to those to which alkali metal ions and alkaline earth metal ions were added.
このように、鉛−アンチモンまたは、鉛−アンチモン−
すずを格子表面に付与し、電解液中にＮ＆“、Ｍｇ２＋
添加することにより相乗効果があり、充電電流、充電受
入性が改善された。Thus, lead-antimony or lead-antimony-
Tin is applied to the lattice surface, and N & “, Mg2+ is added to the electrolyte.
By adding it, there was a synergistic effect, and the charging current and charging acceptability were improved.
発明の効果
以上のように、本発明では優れたメンテナンスフリー性
、高温、深い放電での寿命特性を維持しつつ、自己放電
特性、過放電放置後の充電受入性を改善することができ
、その工業的価値は非常に太きい。Effects of the Invention As described above, the present invention can improve self-discharge characteristics and charge acceptance after over-discharging while maintaining excellent maintenance-free properties and long-life characteristics at high temperatures and deep discharges. The industrial value is very strong.
Claims (2)
面にアンチモンを多く含んだ層を有する電極を用い、か
つ電解液中にアルカリ金属イオンと、アルカリ土類イオ
ンの少なくとも一方を含むことを特徴とした鉛蓄電池。(1) An electrode having a layer containing a large amount of antimony on the surface of a lead-calcium alloy that does not contain antimony is used, and the electrolyte contains at least one of alkali metal ions and alkaline earth ions. lead acid battery.
鉛−アンチモン、または鉛−アンチモン−すず合金であ
ることを特徴とした特許請求の範囲１項記載の鉛蓄電池
。(2) The antimony-rich layer on the electrode surface is
The lead-acid battery according to claim 1, which is made of lead-antimony or lead-antimony-tin alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1181054A JP2808685B2 (en) | 1989-07-13 | 1989-07-13 | Lead storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1181054A JP2808685B2 (en) | 1989-07-13 | 1989-07-13 | Lead storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0346768A true JPH0346768A (en) | 1991-02-28 |
| JP2808685B2 JP2808685B2 (en) | 1998-10-08 |
Family
ID=16093972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1181054A Expired - Lifetime JP2808685B2 (en) | 1989-07-13 | 1989-07-13 | Lead storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2808685B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5929383A (en) * | 1982-08-12 | 1984-02-16 | Shin Kobe Electric Mach Co Ltd | Sealed lead storage battery |
| JPS63213263A (en) * | 1987-02-27 | 1988-09-06 | Shin Kobe Electric Mach Co Ltd | Lead storage battery |
| JPS646374A (en) * | 1987-06-29 | 1989-01-10 | Matsushita Electric Ind Co Ltd | Lead storage battery |
-
1989
- 1989-07-13 JP JP1181054A patent/JP2808685B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5929383A (en) * | 1982-08-12 | 1984-02-16 | Shin Kobe Electric Mach Co Ltd | Sealed lead storage battery |
| JPS63213263A (en) * | 1987-02-27 | 1988-09-06 | Shin Kobe Electric Mach Co Ltd | Lead storage battery |
| JPS646374A (en) * | 1987-06-29 | 1989-01-10 | Matsushita Electric Ind Co Ltd | Lead storage battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2808685B2 (en) | 1998-10-08 |
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