JPS63143757A - Closed type lead storage battery - Google Patents
Closed type lead storage batteryInfo
- Publication number
- JPS63143757A JPS63143757A JP61291818A JP29181886A JPS63143757A JP S63143757 A JPS63143757 A JP S63143757A JP 61291818 A JP61291818 A JP 61291818A JP 29181886 A JP29181886 A JP 29181886A JP S63143757 A JPS63143757 A JP S63143757A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- battery
- electrode plate
- lead
- oxygen gas
- 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.)
- Pending
Links
- 239000002253 acid Substances 0.000 claims description 14
- 239000004020 conductor Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 13
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000007423 decrease Effects 0.000 abstract description 4
- 239000004615 ingredient Substances 0.000 abstract 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052924 anglesite Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004904 shortening Methods 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
-
- 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
- Secondary Cells (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、密閉形鉛蓄電池の特に負極に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to the negative electrode of a sealed lead acid battery.
従来の技術
近年、ポータプルＶＴＲ，小型電気掃除機等の普及に伴
い、電池の需要が伸びてきた。これらのコードレス機器
の電源として、繰り返しの使用が可能で、高出力で、経
済的にも安価な密閉形鉛蓄電池が急速に普及してきた。BACKGROUND OF THE INVENTION In recent years, with the spread of portable VTRs, small vacuum cleaners, etc., the demand for batteries has increased. Sealed lead-acid batteries, which can be used repeatedly, have high output, and are economically inexpensive, have rapidly become popular as power sources for these cordless devices.
第３図は従来の密閉形鉛蓄電池のセルの縦断面の略図を
示すものである。第３図において、１０は正極板、１１
は負極板、１２はセパレータで、ガラス繊維を主成分と
している。１３は電槽で、耐硫酸性を有するポリプロピ
レン製からなる。１４は正極端子、１５は負極端子、１
６は電槽上部に設けたガス抜き弁であり、通常電槽１３
は密閉構造となっている。電解液としては、比重１．３
０の希硫酸が正極、負極、及びセパレータに保持されて
いる。FIG. 3 shows a schematic longitudinal cross-sectional view of a cell of a conventional sealed lead-acid battery. In FIG. 3, 10 is a positive electrode plate, 11
1 is a negative electrode plate, and 12 is a separator, which is mainly composed of glass fiber. 13 is a battery case made of polypropylene having sulfuric acid resistance. 14 is a positive terminal, 15 is a negative terminal, 1
6 is a gas vent valve installed at the top of the battery case, which is normally installed at the top of the battery case 13.
has a closed structure. As an electrolyte, the specific gravity is 1.3
0 dilute sulfuric acid is held on the positive electrode, negative electrode, and separator.
以上のように構成された密閉形鉛蓄電池の密閉化方式と
して、充電末期、あるいは過充電時に正極で発生する酸
素ガスが、下式に示すような酸素サイクル反応によって
水に還元される。In the sealing method of the sealed lead-acid battery configured as described above, oxygen gas generated at the positive electrode at the end of charging or during overcharging is reduced to water by an oxygen cycle reaction as shown in the following formula.
（１） Ｈ２Ｏ−一→２Ｈ＋＋＋０２＋２０（２Ｊ
Ｐｂ＋＋ｏ２＋ｒｉ２Ｓｏ４−ｍ−→ ＰｂＳＯ４＋
Ｈ２゜（３） Ｐｂ５Ｏ＋２Ｈ＋＋２ｅ−一−→Ｐｂ
十Ｈ２Ｓｏ４すなわち、充電末期あるいは過充電時には
、式（１）で示すところの水の電気分解が起こり、正極
上で酸素ガスが発生する。この酸素ガスは負極に達し、
負極上で式（２！ｌに示す反応によって水に還元される
。(1) H2O-1→2H+++02+20(2J
Pb++o2+ri2So4-m-→ PbSO4+
H2゜(3) Pb5O+2H++2e-1-→Pb
In other words, at the end of charging or during overcharging, electrolysis of water as shown in equation (1) occurs, and oxygen gas is generated on the positive electrode. This oxygen gas reaches the negative electrode,
It is reduced to water on the negative electrode by the reaction shown in formula (2!l).
それと同時に硫酸鉛が生成されるが、式（３）の充電反
応によって硫酸鉛は鉛に還元される。この反応によって
式（１）の負極上で発生すべき水素イオンが消費される
為、負極上での水素ガスの発生が防止されるものである
。即ちこれにより、鉛蓄電池の密閉化が可能となった。At the same time, lead sulfate is generated, but the lead sulfate is reduced to lead by the charging reaction of equation (3). This reaction consumes the hydrogen ions that should be generated on the negative electrode according to formula (1), thereby preventing the generation of hydrogen gas on the negative electrode. In other words, this has made it possible to seal lead-acid batteries.
発明が解決しようとする問題点
このような従来の構成では上記の酸素サイクル反応に基
づく酸素ガスの吸収は、充電にさほど関与しない負極の
電槽に対面した一方の表面で主に起こるため、硫酸鉛は
負極板の電槽に面した表面から生成されていく。この硫
酸鉛は鉛へと還元されるが、充電、放電を繰り返したり
、長期にわたって充電を続けると、電気化学的に不活性
な硫酸鉛が増加し、鉛に還元しにくくなる。そのため、
負極は充電しにくくなり、結果として電池の容量が減少
し、寿命を縮めるという問題点を有していた。Problems to be Solved by the Invention In such a conventional configuration, the absorption of oxygen gas based on the above oxygen cycle reaction mainly occurs on one surface of the negative electrode facing the battery case, which is not significantly involved in charging. Lead is generated from the surface of the negative electrode plate facing the battery case. This lead sulfate is reduced to lead, but if charging and discharging are repeated or if charging is continued for a long period of time, the amount of electrochemically inactive lead sulfate increases, making it difficult to reduce to lead. Therefore,
The problem is that the negative electrode becomes difficult to charge, resulting in a decrease in battery capacity and shortened battery life.
本発明は上記従来の問題点を解決するもので、密閉形鉛
蓄電池の容忙低下および寿命の短縮を抑制することを目
的とするものである。The present invention solves the above-mentioned conventional problems, and aims at suppressing the decrease in capacity and shortening of the life of sealed lead-acid batteries.
問題点を解決するだめの手段
このような問題点を解決するために、本発明の密閉形鉛
蓄電池は、負極板の電槽に対面した一方の表面に、非通
気性の導電性物質を介して、鉛を主成分とした多孔性物
質の層を設けたものである。Means for Solving the Problems In order to solve these problems, the sealed lead-acid battery of the present invention has a non-porous conductive material interposed on one surface of the negative electrode plate facing the battery case. A layer of porous material containing lead as a main component is provided.
作 用
このように構成された電池では、負極板の一方の表面に
設けた鉛を主成分とした多孔性物質中で、正極より発生
した酸素ガスは速やかに吸収される。Function In a battery configured in this manner, oxygen gas generated from the positive electrode is quickly absorbed in a porous material mainly composed of lead provided on one surface of the negative electrode plate.
そして、酸素ガスは通気性のない導電性物質でそれ以上
負極板の内側への侵入が止められ、本来の負極板まで拡
散されない。すなわち負極は本来の充放電のみに使用さ
れ、上記の酸素ガス吸収反応には関与しないことになる
。Oxygen gas is prevented from further invading the inside of the negative electrode plate by a conductive substance with no air permeability, and is not diffused to the original negative electrode plate. That is, the negative electrode is used only for the original charging and discharging, and does not participate in the above oxygen gas absorption reaction.
実施例
以下本発明の一実施例について、図面を参照しながら説
明する。EXAMPLE An example of the present invention will be described below with reference to the drawings.
第１図は、本発明の一実施例における密閉形鉛蓄電池の
セルの縦断面の略図を示すものである。FIG. 1 shows a schematic longitudinal cross-sectional view of a cell of a sealed lead-acid battery according to an embodiment of the present invention.
第１図において、１は正極板であり、厚さ３．３ｔｒｒ
Ｉｎ＋高さ９０ｍｍ、幅３５ｒｒｒｒｎの大きさからな
り、活物質は過酸化鉛を主成分としている。２は負極板
であり、厚さ３．０ｍｍ、高さ９０ｒＩＣＩｎ２幅３５
Ｍの大きさで、活物質は鉛を主成分としている。３はセ
パレータであり、ガラス繊維を主成分としており、必袈
量の電解液を保持している。４は非通気性の導電性物質
としての鉛薄板であり、厚さ１ｒＭｎ、高さ９０ ｒａ
ｎ 、幅３５ｍである。５は鉛を主成分とした多孔性物
質であり、厚さ３．０ ｍｍ、高さ９０咽、幅３６−で
、鉛薄板４を介して負極の電槽に面した表面に設けた層
である。６は耐硫酸性を有するポリプロピレン製の電槽
である。７は正極端子、８は負極端子、９は電槽上部に
設けたガス抜き弁で通常電槽内部を密閉構造に保ってい
る。In Fig. 1, 1 is a positive electrode plate, which has a thickness of 3.3 trr.
It has a height of 90 mm and a width of 35 rrrrn, and the active material is mainly lead peroxide. 2 is a negative electrode plate, thickness 3.0 mm, height 90 r ICIn2 width 35
The active material has lead as a main component. 3 is a separator, which is mainly made of glass fiber and holds a necessary amount of electrolyte. 4 is a thin lead plate as a non-breathable conductive material, with a thickness of 1 rMn and a height of 90 ra.
n, width 35m. 5 is a porous material whose main component is lead, and is 3.0 mm thick, 90 mm high, and 36 mm wide, and is a layer provided on the surface of the negative electrode facing the battery case through a thin lead plate 4. be. 6 is a polypropylene battery case having sulfuric acid resistance. 7 is a positive terminal, 8 is a negative terminal, and 9 is a gas vent valve provided at the top of the battery case, which normally maintains the inside of the battery case in a sealed structure.
電解液としては、比重１．３０の希硫酸を使用した。Dilute sulfuric acid with a specific gravity of 1.30 was used as the electrolyte.
次に、第３図に示す従来の密閉形鉛蓄電池を電池Ｂとし
、本発明の密閉形鉛蓄電池を電池Ａとして、正極、負極
の放電容量は共に１．３Ａｈとし、これらの電池を１３
０ｍＡ（１／１０Ｃ）の定電流で、電圧が１．７５Ｖに
達するまで放電を行ない、伏いて１３０ｍＡ（１／１０
Ｃ）の定電流で１２時間（放電容量の１２０％ ）充電
するのを１サイクルとし、これを繰シ返して行なった。Next, the conventional sealed lead-acid battery shown in FIG. 3 is designated as battery B, the sealed lead-acid battery of the present invention is designated as battery A, the discharge capacity of both the positive electrode and the negative electrode is 1.3 Ah, and these batteries are
Discharge at a constant current of 0mA (1/10C) until the voltage reaches 1.75V, then turn it upside down and discharge at 130mA (1/10C).
One cycle consisted of charging at a constant current of C) for 12 hours (120% of the discharge capacity), and this cycle was repeated.
第２図は、電池へ、Ｂのサイクルに伴う放電容量の変化
を示す。従来電池Ｂでは前記のように負極に回復しない
電気化学的に不活性な硫酸鉛が徐々に増加するため、電
池の放電容量が低下し、約２００サイクルで初期容量の
６０％となった。これに対し本発明の電池Ａでは、初期
の容量の５０チとなるのは約２８０サイクルであり、従
来電池Ｂに比較して寿命が長くなっている。これは、本
発明では負極板は本来の充放電のみンて使用され、酸素
ガス吸収が不充分なために起こるサイクル寿命の劣化が
従来より少なかったものと考えられる。FIG. 2 shows the change in discharge capacity of the battery as B cycles. In conventional battery B, as described above, electrochemically inert lead sulfate that does not recover to the negative electrode gradually increases, so the discharge capacity of the battery decreases and reaches 60% of the initial capacity after about 200 cycles. On the other hand, in the battery A of the present invention, it takes about 280 cycles to reach the initial capacity of 50 cm, and the life span is longer than that of the conventional battery B. This is considered to be because, in the present invention, the negative electrode plate is used only for its original charging and discharging purposes, and the deterioration in cycle life caused by insufficient oxygen gas absorption is less than in the past.
なお、本実施例では正極板、逍極板とも各１枚の構成と
したが、正極、負極とも何枚にしてもよく、その場合に
は極板群最外側の負極板の電槽と対面する一方の表面に
同様な措置を施せばよい。In this example, there is one positive electrode plate and one negative electrode plate, but any number of positive electrode plates and negative electrode plates may be used. In that case, the outermost negative electrode plate of the electrode group faces the battery case. Similar measures can be taken on one surface.
発明の効果
以上のように本発明によれば、負極板の電槽に対面した
一方の表面に、非通気性の導電性物質を介して、鉛を主
成分とした多孔性物質の層を設けることにより、この層
での酸素ガス消失を図って、充放電によるサイクル寿命
を向上させるという効果が得られる。Effects of the Invention As described above, according to the present invention, a layer of a porous material mainly composed of lead is provided on one surface of the negative electrode plate facing the battery case via a non-porous conductive material. By doing so, it is possible to achieve the effect of eliminating oxygen gas in this layer and improving the cycle life due to charging and discharging.
第１図は本発明の実施例における密閉形鉛蓄電池の概要
を示す断面略図、第２図は１３０ｍＡでの充放電サイク
ルによる容量劣化の比較図、第３図は従来の密閉形鉛蓄
電池の概要を示す断面略図である。
１・・・・・・正極板、２・・・・・・負極板、４・・
・・・・非通気性の導電性物質、５・・・・・・多孔性
物質、６・・・・・・電槽。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名第
１ 図 イ〜−−正ガ猥２−＊
ｙ、及
４〜４受粧ｓ簀
５− 勿り秩 “Fig. 1 is a schematic cross-sectional diagram showing the outline of a sealed lead-acid battery according to an embodiment of the present invention, Fig. 2 is a comparison diagram of capacity deterioration due to charge/discharge cycles at 130 mA, and Fig. 3 is an outline of a conventional sealed lead-acid battery. FIG. 1...Positive electrode plate, 2...Negative electrode plate, 4...
... Non-breathable conductive material, 5 ... Porous material, 6 ... Battery container. Name of agent: Patent attorney Toshio Nakao and 1 other person
1 Figure I~--- Positive Gashii 2-*
y, and 4~4 makeups 5- Nakurichichi “
Claims (2)
の導電性物質を介して、鉛を主成分とした多孔性物質の
層を設けたことを特徴とする密閉形鉛蓄電池。(1) A sealed lead-acid battery characterized in that a layer of a porous material mainly composed of lead is provided on one surface of the negative electrode plate facing the battery case via a non-breathable conductive material. .
範囲第１項記載の密閉形鉛蓄電池。(2) The sealed lead-acid battery according to claim 1, wherein the non-porous conductive material is a thin lead plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61291818A JPS63143757A (en) | 1986-12-08 | 1986-12-08 | Closed type lead storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61291818A JPS63143757A (en) | 1986-12-08 | 1986-12-08 | Closed type lead storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63143757A true JPS63143757A (en) | 1988-06-16 |
Family
ID=17773813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61291818A Pending JPS63143757A (en) | 1986-12-08 | 1986-12-08 | Closed type lead storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63143757A (en) |
-
1986
- 1986-12-08 JP JP61291818A patent/JPS63143757A/en active Pending
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