JP2867571B2 - Sealed metal oxide / hydrogen storage battery - Google Patents
Sealed metal oxide / hydrogen storage batteryInfo
- Publication number
- JP2867571B2 JP2867571B2 JP2076002A JP7600290A JP2867571B2 JP 2867571 B2 JP2867571 B2 JP 2867571B2 JP 2076002 A JP2076002 A JP 2076002A JP 7600290 A JP7600290 A JP 7600290A JP 2867571 B2 JP2867571 B2 JP 2867571B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- metal oxide
- battery
- storage battery
- 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.)
- Expired - Fee Related
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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
-
- 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
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、水素吸蔵合金を負極材料とし、金属酸化物
電極を正極とする密閉形金属酸化物・水素蓄電池の改良
に関する。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a sealed metal oxide / hydrogen storage battery using a hydrogen storage alloy as a negative electrode material and a metal oxide electrode as a positive electrode.
従来の技術 従来、負極材料として水素吸蔵合金を用いたこの種の
アルカリ蓄電池は、高エネルギー密度，低公害電池とし
て注目され、金属酸化物正極との組合せによる密閉形金
属酸化物・水素蓄電池が提案されている。2. Description of the Related Art Conventionally, this type of alkaline storage battery using a hydrogen storage alloy as a negative electrode material has attracted attention as a high energy density, low pollution battery, and a sealed metal oxide / hydrogen storage battery combined with a metal oxide positive electrode has been proposed. Have been.
水素吸蔵合金は使用時に電解液中で酸化されやすく、
通常その表面に水酸化物が形成され、次第に電極容量が
減少してやがて寿命に達する。そして、密閉形金属酸化
物・水素蓄電池では、過充電時に金属酸化物例えば、ニ
ッケル正極から酸素が発生するが、上述したように水素
吸蔵合金の劣化が起こると、酸素と合金が吸蔵している
水素との反応が妨げられ、酸素が吸収されなくなる。さ
らに、水素吸蔵合金負極から水素が発生するようになる
ため、電池内圧を上昇させる原因となる。The hydrogen storage alloy is easily oxidized in the electrolyte during use,
Usually, a hydroxide is formed on the surface, and the electrode capacity gradually decreases, and the life is eventually reached. In a sealed metal oxide / hydrogen storage battery, oxygen is generated from a metal oxide such as a nickel positive electrode at the time of overcharge, but when the hydrogen storage alloy is deteriorated as described above, the oxygen and the alloy are occluded. Reaction with hydrogen is hindered and oxygen is no longer absorbed. Further, hydrogen is generated from the negative electrode of the hydrogen storage alloy, which causes an increase in battery internal pressure.
従来、上記のような不都合を解消するため、負極に触
媒を添加する方法が提案されている（特開昭62−291862
号公報）。しかし、これは水素吸蔵合金粉末、触媒およ
び結合剤等で水素吸蔵合金負極を形成したものであり、
この方法では、とくに高率充電時において、触媒性能を
最大限に発揮させることが困難であり、充分な効果を発
揮させるには多量の触媒物質が必要であった。Conventionally, a method of adding a catalyst to a negative electrode has been proposed in order to solve the above-mentioned inconvenience (Japanese Patent Application Laid-Open No. 62-291862).
No.). However, this is a hydrogen storage alloy negative electrode formed with a hydrogen storage alloy powder, a catalyst and a binder, etc.
In this method, it is difficult to maximize the catalytic performance, particularly at the time of high-rate charging, and a large amount of a catalytic substance is required to exhibit a sufficient effect.
発明が解決しようとする課題 本発明は、上記問題点を解決するためになされたもの
であり、電解液中での水素吸蔵合金の酸化を防止して電
池寿命を延ばすとともに、電池内で発生する酸素および
水素による電池内圧の上昇を防止することができる密閉
形金属酸化物・水素蓄電池を提供することを目的とす
る。Problems to be Solved by the Invention The present invention has been made in order to solve the above-mentioned problems, and prevents oxidation of a hydrogen storage alloy in an electrolytic solution to extend battery life, and is generated in a battery. An object of the present invention is to provide a sealed metal oxide / hydrogen storage battery that can prevent an increase in battery internal pressure due to oxygen and hydrogen.
課題を解決するための手段 本発明の密閉形金属酸化物・水素蓄電池は、金属酸化
物例えば、ニッケル酸化物，カドミウム酸化物等からな
る正極、水素吸蔵合金電極からなる負極の間にセパレー
タを介在させた電極体と、ハニカム構造からなる活性炭
を担体とした触媒体とで構成し、これらを密閉容器に収
容し、アルカリ水溶液を電解液として注入し密閉したこ
とを特徴とするものである。Means for Solving the Problems In the sealed metal oxide / hydrogen storage battery of the present invention, a separator is interposed between a positive electrode made of a metal oxide such as nickel oxide and cadmium oxide and a negative electrode made of a hydrogen storage alloy electrode. It is characterized by comprising an electrode body formed as described above and a catalyst body using activated carbon having a honeycomb structure as a carrier, and these are housed in a closed container, and an alkaline aqueous solution is injected as an electrolytic solution and sealed.
さらに、前記活性炭担体に担持する触媒としては、例
えば、白金（Pt），パラジウム（Pd），ロジウム（R
d），ルテニウム（Ru）から選ばれる少なくとも１種の
金属を担持させたものを挙げることができる。Further, as the catalyst supported on the activated carbon carrier, for example, platinum (Pt), palladium (Pd), rhodium (R
d) and those carrying at least one metal selected from ruthenium (Ru).
作用 このような密閉形金属酸化物・水素蓄電池によれば、
高活性な触媒が電池内に配置されているため、電池内で
発生する酸素と水素との反応を効率よく促進させ、迅速
に水にもどすことができる。従って従来問題であった電
池内圧の上昇を抑制し、安全性を高めるのみでなく、電
池寿命をも向上させることができる。Action According to such a sealed metal oxide / hydrogen storage battery,
Since the highly active catalyst is disposed in the battery, the reaction between oxygen and hydrogen generated in the battery can be efficiently promoted and the water can be quickly returned to water. Therefore, it is possible to suppress the increase in the internal pressure of the battery, which has been a problem in the related art, and to improve the safety as well as the battery life.
実施例 以下、本発明の実施例を図面に従い説明する。負極に
使用する水素吸蔵合金としては、MmNi4.2Mn8.8（Mmはミ
シュメタル）を選び、この合金のインゴットを耐圧容器
内に収容して、水素の吸蔵および除去を行い活性化処理
を施した。この水素吸蔵合金粉末に適量（3wt％〜5wt
％）のポリビニルアルコールを結着剤として加え、よく
混合し、発泡状金属多孔体内に充填し、加圧乾燥後リー
ドを取り付け負極電極とした。また、正極には公知の焼
結形ニッケルを用い、セパレータ（ポリプロピレン製フ
ィルムおよびナイロン製フィルムより構成）を介在させ
全体を渦巻状に巻いて電極体を形成させた。さらに活性
炭を担体とした触媒体を組み込み、アルカリ水溶液（30
％KOH）電解液を注入し密閉形金属酸化物・水素蓄電池
を作製した。前記活性炭には、ヤシガラ粒状炭（約¢２
〜3mmのタブレット状）と、ヤシガラ活性炭粉末と結着
剤（メチルセルロース）および、ある種の成形バインダ
ーを添加し、水とともに混練後、ハニカム状に押し出し
成形したハニカム構造体を、ヘリウム（He）ガス雰囲気
で800℃の温度で処理し得られたハニカム状活性炭を使
用した。また、触媒物質としてはパラジウム（Pd）を用
い、活性炭担体に対し0.1wt％担持させた。担持方法
は、所定濃度の塩化パラジウム水溶液（PdCl2）を調製
し、これに活性炭担体を浸漬させ、乾燥後、水素10％の
窒素ガス気流中において200℃で活性化処理を施して作
製した。さらに、これらの活性炭を担体とする触媒をフ
ッ素樹脂による撥水処理を施したものもまた同時に作製
した。なお、撥水処理は、フッ素樹脂の懸濁液（ダイキ
ン工業製 商品名 Ｄ−１）に浸漬後、100℃で乾燥し
て調製した。Embodiments Hereinafter, embodiments of the present invention will be described with reference to the drawings. As a hydrogen storage alloy used for the negative electrode, MmNi 4.2 Mn 8.8 (Mm is Misch metal) was selected, an ingot of this alloy was housed in a pressure-resistant container, and hydrogen was stored and removed to perform an activation treatment. An appropriate amount (3 wt% to 5 wt%)
%) Of polyvinyl alcohol was added as a binder, mixed well, filled in a foamed metal porous body, dried under pressure, and a lead was attached to form a negative electrode. A known sintered nickel was used for the positive electrode, and the whole was spirally wound with a separator (composed of a polypropylene film and a nylon film) interposed therebetween to form an electrode body. In addition, a catalyst using activated carbon as a carrier is incorporated, and an alkaline aqueous solution (30
% KOH) electrolyte was injected to produce a sealed metal oxide / hydrogen storage battery. The activated carbon includes coconut shell granular charcoal (about $ 2
33 mm tablet), coconut shell activated carbon powder, a binder (methylcellulose), and a certain molding binder were added, kneaded with water, and extruded into a honeycomb shape to form a honeycomb structure. Honeycomb activated carbon obtained by treatment at a temperature of 800 ° C. in an atmosphere was used. Also, palladium (Pd) was used as a catalyst substance, and 0.1 wt% was supported on an activated carbon carrier. The supporting method was prepared by preparing an aqueous solution of palladium chloride (PdCl 2 ) having a predetermined concentration, immersing an activated carbon carrier in the aqueous solution, drying the coating, and then performing an activation treatment in a nitrogen gas stream of 10% hydrogen at 200 ° C. Further, those obtained by subjecting these activated carbon-supported catalysts to a water-repellent treatment with a fluororesin were also produced at the same time. The water-repellent treatment was prepared by immersing the resin in a fluororesin suspension (D-1 manufactured by Daikin Industries, Ltd.) and drying at 100 ° C.
電極体と触媒体の本実施例の具体的な構成は、第１図
の単２形の密閉形金属酸化物・水素蓄電池で示した。The specific structure of the present embodiment of the electrode body and the catalyst body was shown in the form of a C-type sealed metal oxide / hydrogen storage battery of FIG.
第１図において、水素吸蔵合金からなる負極板１とニ
ッケル正極２はセパレータ３を介して渦巻状に巻かれて
ケース４内に配置されている。この電極体上には絶縁板
５を介して、電池内に発生する水素ガスおよび酸素ガス
を水に変換するための活性炭担体からなる触媒体６を入
れて安全弁を有する封口板７でケースを閉じることで密
閉化されている。８は正極リード９と接続している正極
端子である。In FIG. 1, a negative electrode plate 1 made of a hydrogen storage alloy and a nickel positive electrode 2 are spirally wound via a separator 3 and arranged in a case 4. A catalyst body 6 made of an activated carbon carrier for converting hydrogen gas and oxygen gas generated in the battery into water is put on the electrode body via an insulating plate 5 and the case is closed with a sealing plate 7 having a safety valve. It is hermetically sealed. Reference numeral 8 denotes a positive electrode terminal connected to the positive electrode lead 9.
第２図に本実施例の密閉形ニッケル・水素蓄電池にお
ける充放電サイクルと電池内圧の変化を示した。蓄電池
の充放電条件は、600mAで５時間充填し、400mAで放電し
た。この時の充放電サイクル試験の温度は室温とし、各
電池の充放電サイクル毎の内圧を圧力センサーにより測
定したものである。その結果、ａで示す本発明のハニカ
ム状活性炭からなる触媒体を使用した電池の内圧は、各
サイクル（50サイクル,100サイクル,150サイクル,200サ
イクル,250サイクル）において、電池内圧の目標値5kg/
cm2（安全弁の作動値）に対し、ヤシガラ粒状活性炭よ
り作製した電池ｂの内圧よりも低い値を示した。FIG. 2 shows the charge / discharge cycle and the change in battery internal pressure in the sealed nickel-metal hydride storage battery of this embodiment. The battery was charged and discharged at 600 mA for 5 hours and discharged at 400 mA. The temperature of the charge / discharge cycle test at this time was room temperature, and the internal pressure of each battery in each charge / discharge cycle was measured by a pressure sensor. As a result, in each cycle (50 cycles, 100 cycles, 150 cycles, 200 cycles, and 250 cycles), the internal pressure of the battery using the catalyst body made of the honeycomb-shaped activated carbon of the present invention indicated by a was set to a target value of 5 kg of the battery internal pressure. /
With respect to cm 2 (operation value of the safety valve), the value was lower than the internal pressure of the battery b made of coconut shell granular activated carbon.
また、第３図に示す如く、撥水処理を施すことによっ
ても電池内圧を低くする効果が認められた。Further, as shown in FIG. 3, the effect of lowering the internal pressure of the battery was also recognized by performing the water-repellent treatment.
以上、本発明を実施例に従い説明したが特に、負極材
料，正極材料およびセパレータ材料等は、これらに限定
されるものではない。As described above, the present invention has been described in accordance with the embodiments. In particular, the negative electrode material, the positive electrode material, the separator material, and the like are not limited to these.
発明の効果 以上記述した如く本発明によれば、電池寿命が長く、
電池内で発生する酸素および水素による電池内圧の上昇
を防止することができる密閉形金属酸化物・水素蓄電池
を提供できるものである。According to the present invention as described above, the battery life is long,
An object of the present invention is to provide a sealed metal oxide / hydrogen storage battery capable of preventing an increase in battery internal pressure due to oxygen and hydrogen generated in the battery.
第１図は本発明の実施例における触媒体を用いた密閉形
金属酸化物・水素蓄電池の構成を示す断面略図、第２
図，第３図は本実施例の電池の充放電サイクルに伴う電
池内圧変化を示す図である。 １……負極、２……正極、３……セパレータ、４……電
池ケース、５……絶縁板、６……触媒体、７……封口
板、８……正極端子、９……正極リード。FIG. 1 is a schematic sectional view showing the structure of a sealed metal oxide / hydrogen storage battery using a catalyst according to an embodiment of the present invention.
FIGS. 3A and 3B are diagrams showing changes in the internal pressure of the battery according to the charge / discharge cycle of the battery of this embodiment. DESCRIPTION OF SYMBOLS 1 ... Negative electrode, 2 ... Positive electrode, 3 ... Separator, 4 ... Battery case, 5 ... Insulating plate, 6 ... Catalyst body, 7 ... Sealing plate, 8 ... Positive electrode terminal, 9 ... Positive electrode lead .
───────────────────────────────────────────────────── フロントページの続き (72)発明者 門内 英治 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (56)参考文献 特開 昭62−272475（ＪＰ，Ａ) 特開 昭49−44240（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 10/24 - 10/34 H01M 10/52──────────────────────────────────────────────────続 き Continued on the front page (72) Eiji Kaduchi, Inventor 1006 Odakadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) References JP-A-62-272475 (JP, A) JP-A-49- 44240 (JP, A) (58) Field surveyed (Int. Cl. 6 , DB name) H01M 10/24-10/34 H01M 10/52
Claims (2)
金電極からなる負極との間にセパレータを介在させた電
極体と、ハニカム構造からなる活性炭を担体とした触媒
体とで構成され、アルカリ水溶液を電解液としたことを
特徴とする密閉形金属酸化物・水素蓄電池。An electrode body comprising a separator between a positive electrode comprising a metal oxide electrode and a negative electrode comprising a hydrogen storage alloy electrode; and a catalyst body comprising activated carbon having a honeycomb structure as a carrier. A sealed metal oxide / hydrogen storage battery characterized by using an aqueous solution as an electrolyte.
樹脂により撥水性処理を施したことを特徴とする特許請
求の範囲第１項記載の密閉形金属酸化物・水素蓄電池。2. The sealed metal oxide / hydrogen storage battery according to claim 1, wherein the surface of the catalyst body is subjected to a water-repellent treatment with a fluorine resin or a silicon resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2076002A JP2867571B2 (en) | 1990-03-26 | 1990-03-26 | Sealed metal oxide / hydrogen storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2076002A JP2867571B2 (en) | 1990-03-26 | 1990-03-26 | Sealed metal oxide / hydrogen storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03274678A JPH03274678A (en) | 1991-12-05 |
| JP2867571B2 true JP2867571B2 (en) | 1999-03-08 |
Family
ID=13592599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2076002A Expired - Fee Related JP2867571B2 (en) | 1990-03-26 | 1990-03-26 | Sealed metal oxide / hydrogen storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2867571B2 (en) |
-
1990
- 1990-03-26 JP JP2076002A patent/JP2867571B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03274678A (en) | 1991-12-05 |
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