JPH077678B2 - Cathode gas absorption type lead dioxide-zinc acid battery - Google Patents
Cathode gas absorption type lead dioxide-zinc acid batteryInfo
- Publication number
- JPH077678B2 JPH077678B2 JP60187154A JP18715485A JPH077678B2 JP H077678 B2 JPH077678 B2 JP H077678B2 JP 60187154 A JP60187154 A JP 60187154A JP 18715485 A JP18715485 A JP 18715485A JP H077678 B2 JPH077678 B2 JP H077678B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- lead dioxide
- battery
- cathode gas
- gas absorption
- 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
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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/20—Semi-lead accumulators, i.e. accumulators in which only one electrode contains lead
-
- 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)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、二酸化鉛と亜鉛を主電極材とする密閉機能を
有する充放電可能な陰極ガス吸収式二酸化鉛−亜鉛酸電
池に関する。TECHNICAL FIELD The present invention relates to a cathode gas absorption type lead dioxide-zinc acid battery which uses lead dioxide and zinc as main electrode materials and has a sealing function and which can be charged and discharged.
従来の技術 従来鉛蓄電池の密閉化や高容量化についての改善策（密
閉化は、負極Pb極へのガス吸収反応、高容量化は、活物
質の利用率の向上等）が提案されているが、特にエネル
ギー密度の向上に対し、活物質の利用率向上には限界が
あり、蓄電池の超電力の増加等については、特策がない
状態である。Conventional technology Conventional measures for sealing and increasing the capacity of lead-acid batteries have been proposed (for sealing, gas absorption reaction to the negative electrode Pb electrode, for increasing capacity, improving the utilization rate of active material, etc.). However, there is a limit to the improvement of the utilization rate of the active material with respect to the improvement of the energy density, and there is no special measure for the increase of super power of the storage battery.
発明が解決しようとする問題点 理論的、あるいは、ビーカワーク的組合わせとしては，
起電力を上げるために、PbO2−Zn電池、PbO2−Li電池等
が知られているが、これらの組合わせ電池の場合、負極
活物質の放電生成物が酸溶解物となることや、電池放電
中に負極活物質が電解液に溶解してゆく、即ち自己放電
が著しく進行すること、あるいは、充放電を繰返して行
くと、負極活物質が、デンドライト（樹枝状）となり、
正極と短縮を起す等の問題点があり、充放電可能な電池
として実用化に到っていない。Problems to be Solved by the Invention As a theoretical or beakerwork combination,
In order to increase the electromotive force, PbO 2 -Zn battery, PbO 2 is -Li battery or the like is known, in these cases the combination battery, the discharge product of the anode active material is acid digest and, When the negative electrode active material is dissolved in the electrolytic solution during battery discharge, that is, when self-discharge remarkably progresses, or when charging and discharging are repeated, the negative electrode active material becomes dendrite (dendritic),
There are problems such as shortening with the positive electrode, and it has not been put to practical use as a chargeable / dischargeable battery.
問題点を解決するための手段 一般に、上記溶解に関する反応抑制のために負極活物質
表面を水銀によって、アマルガム化する手段はよく知ら
れている。しかし、寿命電池の廃棄時の水銀汚染につい
ては、重大な問題があり、他の一次電池や二次電池にお
いてもその使用を排除しつつある現状である。本発明は
かかる問題点を解決するものであり、さらに従来の鉛蓄
電池よりも、高電圧、高エネルギー密度、さらに新に密
閉機能を有する新形鉛蓄電池である。すなわち、正極に
二酸化鉛、負極に亜鉛を主電極材料とし、希硫酸を電解
液とする陰極ガス吸収式二酸化鉛−亜鉛酸電池であっ
て、電解液を正極に含浸させると共に電解液保持体もし
くは隔離体あるいはゲル状物質に保持した状態に構成し
て、負極および負極周辺の電解液を極力少量ならしめた
ことにより、亜鉛の溶解度を低下せしめて自己放電とデ
ンドライト生成を防止すると共に、陰極ガス吸収機能を
付与して電解液の減少を防止し初めて、従来の鉛蓄電池
に比べ高電圧、高エネルギー密度の実用に供しうる二酸
化鉛−亜鉛酸電池が得られるようになったものである。Means for Solving the Problems In general, means for amalgamating the surface of the negative electrode active material with mercury in order to suppress the reaction relating to the dissolution is well known. However, there is a serious problem regarding mercury pollution at the time of disposal of a long-life battery, and its use is being excluded from other primary batteries and secondary batteries. The present invention solves such a problem, and is a new lead storage battery having a higher voltage, a higher energy density, and a new sealing function than the conventional lead storage battery. That is, a cathode gas absorption type lead dioxide-zinc acid battery in which lead dioxide is used for the positive electrode, zinc is used as the main electrode material for the negative electrode, and dilute sulfuric acid is used as the electrolytic solution. It is configured to be held in a separator or gel-like substance, and the electrolyte solution around the negative electrode and the negative electrode is made as small as possible, which reduces the solubility of zinc and prevents self-discharge and dendrite formation, and at the same time, the cathode gas. For the first time, it is possible to obtain a lead dioxide-zinc acid battery which has a higher voltage and a higher energy density than conventional lead storage batteries and which can be put to practical use for the first time by providing an absorbing function and preventing the decrease of the electrolytic solution.
作用 本発明の基本的作用原理について説明する。Action The basic action principle of the present invention will be described.
先ず、亜鉛を負極活物質として用いる場合、従来の構成
からなる鉛蓄電池の形成を採れば、電解液、すなわち希
硫酸が、負極および負極周辺に多く存在（浸漬）する状
態となり、亜鉛の溶解を促進する状態にある。First, when zinc is used as the negative electrode active material, if a lead storage battery having a conventional configuration is adopted, a large amount of electrolytic solution, that is, dilute sulfuric acid, exists (immerses) around the negative electrode and the negative electrode, and the zinc is not dissolved. It is in a state of promotion.
従来この溶解を抑制する手段として、水銀によって、亜
鉛極をアマルガム化する方法が提案されている。しか
し、廃電池にHgが残留することを避けるために、新たな
観点にたち、対応を試みた。すなわち、負極および負極
周辺の電解液量を極力少量ならしめて、亜鉛の溶解度を
低下せしめると共に、充電中に、正極から発生する酸素
ガスの吸収をし易くすることにより、少量電解液の減少
を防止することを期するものである。Conventionally, as a means for suppressing this dissolution, a method of converting a zinc electrode into an amalgam by using mercury has been proposed. However, in order to avoid Hg remaining in the waste battery, we tried to take a new approach. That is, the amount of electrolyte around the negative electrode and the negative electrode is made as small as possible to reduce the solubility of zinc, and at the same time, it is easy to absorb the oxygen gas generated from the positive electrode during charging, thus preventing a decrease in the amount of electrolyte. It is intended to be done.
実施例 本発明の実施例について説明する。Example An example of the present invention will be described.
第１図は、本発明の電池であり、１は正極（二酸化
鉛）、２は負極（亜鉛）、３は極細のガラス繊維体で、
硫酸電解液（SP、Gr1.300）を含浸している。硫酸電解
液は、二酸化鉛の中にも遊離液を有さぬ程度に含まれて
いる。４は合成樹脂例えばアクリロントリル・ブタンジ
エン・スチレンコポリマーからなる電槽で、フッ素ゴム
の安全弁５を有し、減圧時は閉弁し、空気の流入を防止
する機能を有している。６は端子部、６′は一端子部
である。1 is a battery of the present invention, 1 is a positive electrode (lead dioxide), 2 is a negative electrode (zinc), 3 is an ultrafine glass fiber body,
Impregnated with sulfuric acid electrolyte (SP, Gr1.300). The sulfuric acid electrolyte is contained in lead dioxide to the extent that it does not have a free liquid. Reference numeral 4 is a battery case made of a synthetic resin such as acrylontolyl-butanediene-styrene copolymer, which has a safety valve 5 of fluororubber, which is closed at the time of depressurization and has a function of preventing the inflow of air. 6 is a terminal portion, and 6'is one terminal portion.
上記構成の電池は、次式の反応を起し、 充電末期は未解明であるが 陽極（PbO2） 陰極（Zn） 4OH-→O2＋2H2O＋4e- 2Zn＋O2→2ZnO 2ZnO＋4H+＋4e-→Zn＋2H2O ………（２） が想定され、事実上減液や、ガスの排出がない密閉電池
を構成する。The battery having the above structure causes the reaction of the following formula, End of charge is not yet elucidated anode (PbO 2) cathode (Zn) 4OH - → O 2 + 2H 2 O + 4e - 2Zn + O 2 → 2ZnO 2ZnO + 4H + + 4e - → Zn + 2H 2 O ......... (2) is assumed, practically Construct a sealed battery that does not reduce liquid or discharge gas.
本発明電池の性能諸元を従来の鉛蓄電池と比較すると、 従来鉛蓄電池 本発明電池 起 電 力 2.0V/セル 2.5V/セル エネルギー密度 20〜50wh/Kg 40〜80wh/Kg 代表的な特性ではあるが、従来の鉛電池に対し大幅に性
能向上を達成することができた。第２図は、本発明電池
の200mAh、2.5V電池の寿命サイクル試験の結果であり、
300サイクル以上の用途に充分耐えることが判明した。
他の実施例として、電解質に二酸化珪素を主成分として
希硫酸とゲル化したものも用いることができる。また、
繊維体とゲル状電解液の使用も可能である。繊維体はガ
ラスや、合成繊維も使用可能である。特に亜鉛極につい
ては、亜鉛を主成分とする合金や、焼結体、ペースト状
物等適用範囲は広い。希硫酸の比重も液量により、1.10
0〜1.800と広範囲に使用でき、特に限定されることはな
い。When comparing the performance specifications of the battery of the present invention with those of the conventional lead storage battery, the conventional lead storage battery of the present invention has a voltage of 2.0 V / cell 2.5 V / cell energy density of 20 to 50 wh / Kg 40 to 80 wh / Kg. However, we were able to achieve a significant improvement in performance over conventional lead batteries. FIG. 2 is a result of a life cycle test of a 200 mAh, 2.5 V battery of the present invention,
It has been found that it can withstand more than 300 cycles.
As another embodiment, an electrolyte in which silicon dioxide as a main component and gelled with dilute sulfuric acid can be used. Also,
It is also possible to use a fibrous body and a gel electrolyte. As the fibrous body, glass or synthetic fiber can be used. In particular, the zinc electrode has a wide range of applications such as alloys containing zinc as a main component, sintered bodies, and pastes. The specific gravity of dilute sulfuric acid is 1.10 depending on the liquid volume.
It can be used in a wide range of 0 to 1.800 and is not particularly limited.
基本的に、PbO2とZnを電極材料とし、固定化された電解
液の殆どをZn電極およびその周辺以外の部分に保持し、
密閉機能を備えるものである。Basically, PbO 2 and Zn are used as electrode materials, and most of the fixed electrolytic solution is held on the Zn electrode and its surroundings,
It has a sealing function.
発明の効果 本発明の二酸化鉛−亜鉛酸電池は、亜鉛の溶解度を低下
せしめて自己放電とデンドライト生成を防止すると共
に、陰極ガス吸収機能を付与して電解液の減少を防止し
初めて、従来の鉛蓄電池に比べ高電圧、高エネルギー密
度の実用に供しうる二酸化鉛−亜鉛酸電池が得られるよ
うになった。Advantageous Effects of Invention The lead dioxide-zinc acid battery of the present invention reduces the solubility of zinc to prevent self-discharge and dendrite formation, and at the same time prevents the decrease of the electrolytic solution by imparting a cathode gas absorption function. A lead dioxide-zinc acid battery, which has a higher voltage and a higher energy density and can be put to practical use, has been obtained.
第１図は、本発明電池で、（ａ）は外観図、（ｂ）は断
面図、第２図は本発明の200mAh（10HR）2.5V/セル電池
の200mA放電、20mA充電による充放電サイクル試験特性
曲線図である。 1:正極板（PbO2）、2:負極板（Zn）、3:ガラス繊維体、
4:電槽、5:安全弁FIG. 1 is a battery of the present invention, (a) is an external view, (b) is a cross-sectional view, and FIG. 2 is a 200 mAh (10 HR) 2.5 V / cell battery of the present invention, 200 mA discharge, 20 mA charge / discharge cycle It is a test characteristic curve figure. 1: Positive electrode plate (PbO 2 ), 2: Negative electrode plate (Zn), 3: Glass fiber body,
4: Battery case, 5: Safety valve
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小牧 昭夫 東京都新宿区西新宿２丁目１番１号 新神 戸電機株式会社内 審判の合議体 審判長 長瀬 誠 審判官 相沢 旭 審判官 寺本 光生 (56)参考文献 特開 昭58−201270（ＪＰ，Ａ) 特公 昭48−2375（ＪＰ，Ｂ１) 特公 昭42−26516（ＪＰ，Ｂ１) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Komaki 2-1-1, Nishishinjuku, Shinjuku-ku, Tokyo Shin-Kamido Electric Co., Ltd. Judgment panel for referee Makoto Nagase Judge, Asahi Aizawa Judge, Mitsuo Teramoto ( 56) References JP-A-58-201270 (JP, A) JP-B 48-2375 (JP, B1) JP-B 42-26516 (JP, B1)
Claims (1)
とし、希硫酸を電解液とする陰極ガス吸収式二酸化鉛−
亜鉛酸電池であって、 電解液を正極に含浸させると共に電解液保持体もしくは
隔離体あるいはゲル状物質に保持した状態に構成して、
負極および負極周辺の電解液を極力少量ならしめたこと
を特徴とする陰極ガス吸収式二酸化鉛−亜鉛酸電池。1. A cathode gas absorption type lead dioxide which uses lead dioxide for a positive electrode, zinc as a main electrode material for a negative electrode, and dilute sulfuric acid as an electrolytic solution.
A zinc-acid battery, in which the positive electrode is impregnated with the electrolytic solution and the electrolytic solution is held in an electrolytic solution holder or a separator or a gel substance,
A cathode gas absorption type lead dioxide-zinc acid battery characterized in that a small amount of the electrolyte solution around the negative electrode and the negative electrode is filled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60187154A JPH077678B2 (en) | 1985-08-26 | 1985-08-26 | Cathode gas absorption type lead dioxide-zinc acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60187154A JPH077678B2 (en) | 1985-08-26 | 1985-08-26 | Cathode gas absorption type lead dioxide-zinc acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6247976A JPS6247976A (en) | 1987-03-02 |
| JPH077678B2 true JPH077678B2 (en) | 1995-01-30 |
Family
ID=16201065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60187154A Expired - Lifetime JPH077678B2 (en) | 1985-08-26 | 1985-08-26 | Cathode gas absorption type lead dioxide-zinc acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH077678B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58201270A (en) * | 1982-05-18 | 1983-11-24 | Yuasa Battery Co Ltd | Lead-acid battery |
-
1985
- 1985-08-26 JP JP60187154A patent/JPH077678B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6247976A (en) | 1987-03-02 |
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