JPS59181459A - Metal oxide hydrogen battery - Google Patents
Metal oxide hydrogen batteryInfo
- Publication number
- JPS59181459A JPS59181459A JP58053757A JP5375783A JPS59181459A JP S59181459 A JPS59181459 A JP S59181459A JP 58053757 A JP58053757 A JP 58053757A JP 5375783 A JP5375783 A JP 5375783A JP S59181459 A JPS59181459 A JP S59181459A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- hydrogen
- battery
- metal oxide
- pressure
- 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
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
- H01M10/345—Gastight metal hydride 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
Landscapes
- 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】
〔発明の技術分野〕
本発明は、金属酸化物を正極活物質とし、水素を負極活
物質とする、いわゆる金属酸化物・水素電池に係り、さ
らに詳しくは、その中で水素吸蔵金属を主要構成要素と
する水素負極を改良した金属酸化物・水素電池に関する
。[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a so-called metal oxide/hydrogen battery in which a metal oxide is used as a positive electrode active material and hydrogen is used as a negative electrode active material. The present invention relates to a metal oxide/hydrogen battery with an improved hydrogen negative electrode whose main component is a hydrogen-absorbing metal.
水素吸蔵金属を水素極の主要構成要素とする金属酸化物
・水素電池が注目を集めている。これは元来エネルギー
密度の大きなこの電池系を、容積効率的によυ有利にし
、かつより安全に作動させるようにすることにより、特
性的にも信頼性的にも優れた電池を得ることが可能とな
るためである。Metal oxide hydrogen batteries that use hydrogen storage metal as the main component of the hydrogen electrode are attracting attention. By making this battery system, which originally has a high energy density, more advantageous in volumetric efficiency and operating it more safely, it is possible to obtain a battery with excellent characteristics and reliability. This is because it becomes possible.
従来は水素吸蔵金属として、ＬａＮｉ５が最も多く試み
られており、かなり良好な結果が得られている。しかし
ながら、密閉された電池容器内の圧力は、水素吸蔵金属
を使わない場合（≦５０ ｋｇ／ ｃｍｔ）に比較し小
さくなったとはいえ、依然して常温では２〜５ ｋｇ
／ ｃｍ２の値を示していて、例えばニッケルカドミウ
ム電池（０〜１ ｋｇ／ Ｃｍ’ ）に比較すれば高い
圧力であるといえる。電池内の圧力がこのように大気圧
よりも大きいことは、電池容器の構造をある程度強いも
のにする必要がある他に、次の二つの欠点をもつ、一つ
は、電池内の水素気体分子はその分子直径が小さく、そ
のために密閉容器からどうしても徐々に大気へもれやす
く、安全性の面で望ましくないこと、もう一つは、その
結果水素極から吸蔵水素が放出されることになシ、容量
が低下して自己放電を招くことである。Conventionally, LaNi5 has been tried most often as a hydrogen storage metal, and quite good results have been obtained. However, although the pressure inside the sealed battery container is lower than that in the case where hydrogen storage metal is not used (≦50 kg/cmt), it is still 2 to 5 kg/cmt at room temperature.
/cm2, which can be said to be a high pressure compared to, for example, a nickel cadmium battery (0 to 1 kg/cm'). The fact that the pressure inside the battery is higher than atmospheric pressure has the following two drawbacks, in addition to the need to make the structure of the battery container somewhat strong.One is that the hydrogen gas molecules inside the battery Because of its small molecular diameter, it tends to gradually leak into the atmosphere from a closed container, which is undesirable from a safety standpoint.Secondly, as a result, there is no possibility that occluded hydrogen will be released from the hydrogen electrode. , the capacity decreases and self-discharge occurs.
本発明は」１記の欠点を解消するものであり、金が酸化
物・水素電池の電池内圧を保持してＨ２が漏洩する小な
く電池の安全性を確保し、自己放電をも抑えた金属酸化
物・水素電池を提供する事を目的とするものである。The present invention solves the drawbacks mentioned in 1. Gold is a metal that maintains the internal pressure of oxide/hydrogen batteries, ensures battery safety without leaking H2, and also suppresses self-discharge. The purpose is to provide oxide/hydrogen batteries.
本発明け、水素吸蔵金属を主要構成要素とする水素極を
有する金属酸化物・水素電池において、該水素吸蔵金属
として２０℃における平衡プラトー圧力がｌａｔｍ以下
のものを用いたことを特徴とする。The present invention is characterized in that a metal oxide/hydrogen battery having a hydrogen electrode having a hydrogen storage metal as a main component has an equilibrium plateau pressure of latm or less at 20° C. as the hydrogen storage metal.
使用する水素吸蔵金属は、ランタン（Ｌａ）系。The hydrogen storage metal used is lanthanum (La).
ミツシュメタル（Ｍｍ ）系、鉄（Ｆｅ）系、チタン（
Ｔ１）系、バナジウム（Ｖ）系、マグネシウム（Ｍｇ）
系、ニッケル（Ｎｉ）系などいずれでもよく、マたはそ
れら斤いしは他の元素との合金でもよいが、その平衡プ
ラトー圧が２０℃でｌ ａｔｍ以下を示すものであれば
よい。Mitsushi metal (Mm) type, iron (Fe) type, titanium (
T1) type, vanadium (V) type, magnesium (Mg)
The material may be of any type, nickel (Ni) type, etc., or may be alloyed with other elements, as long as its equilibrium plateau pressure is latm or less at 20°C.
具体的には、
ＡＮｉｓ−ｘＭｘ
で示されるものが挙げられる。なお上記において特にＬ
ａＮｉ ５−ｘＩｘの場合はＸ≧０．０７ ＭｍＮ ｉ
３−ｘＦｅＸの場合はＸ≧２．１ 、 ＭｍＮｉｓ−
ｘＭｎｘの場合はＸ≧０．６とする事が好ましい。Specifically, what is shown by ANis-xMx is mentioned. In addition, in the above, especially L
For aNi 5-xIx, X≧0.07 MmN i
In the case of 3-xFeX, X≧2.1, MmNis-
In the case of xMnx, it is preferable that X≧0.6.
さらに具体的にはＬａＮｉ４γＡ７ｏ３．ＭｍＮｉｔｚ
Ｍｒ＋ｏ、ｓが好ましい。More specifically, LaNi4γA7o3. MmNitz
Mr+o, s is preferred.
これらの金属を適当な方法で水素電極とし、一方金属酸
化物電極としては、例えば、酸化銀（ＡｇＯ捷たはＡｇ
２Ｏ）あるいはニッケルオキシ水酸化物（Ｎｉ００Ｈ）
を用いて、これをセパレータを介して密着させて容器内
に収納し、これにアルカリ水溶液を加えてから容器を密
閉して、本発明に係わる金属酸化物・水素電池とするこ
とができる。These metals can be used as hydrogen electrodes by an appropriate method, while metal oxide electrodes can be made using, for example, silver oxide (AgO oxide or Ag
2O) or nickel oxyhydroxide (Ni00H)
The metal oxide/hydrogen battery according to the present invention can be obtained by placing this in a container in close contact with each other via a separator, adding an alkaline aqueous solution to the container, and then sealing the container.
次に本発明を実施例にて説明する。水素吸蔵金属として
ＭｍＮ ｉ ｔｚＭｎ ｏ、ｓを使用する。Next, the present invention will be explained using examples. MmN i tzMno,s is used as the hydrogen storage metal.
まず、ＭｍＮｉ４２Ｍｎｏ、ｓは、この元素組成に示さ
れる属酸元索の容量を、粉末状に破砕した後混合し、真
空アーク溶解炉にて溶解し、均一固溶体を得る。First, MmNi42Mno,s is crushed into a powder having the capacity indicated by this elemental composition, mixed, and melted in a vacuum arc melting furnace to obtain a uniform solid solution.
次に、これを直径５ ｍｍ程度オでに破砕し、次にこれ
をいわゆる活性化処理することにより、水素の吸蔵放出
が容易に行なわれる状態とする。このとき金属は５０〜
１００μｍ程度の粉末状となる。Next, this is crushed to a diameter of about 5 mm, and then subjected to a so-called activation treatment, thereby making it easy to absorb and release hydrogen. At this time, the metal is 50~
It becomes a powder with a size of about 100 μm.
活性化して１００μｍ程度の粉末状となった金属と、ポ
リテトラフルオロエチレン（ＰＴＦＥ）の分散液を混合
して十分に混練した後圧さ０．５ ｍｍのシート状物質
とする。このときの混合比は乾燥状態での値として、金
属： ＰＴＦＥ＝９０ ： １０とした。The activated metal, which has become a powder with a diameter of about 100 μm, and a dispersion of polytetrafluoroethylene (PTFE) are mixed and sufficiently kneaded to form a sheet-like material with a pressure of 0.5 mm. The mixing ratio at this time was metal:PTFE=90:10 as a value in a dry state.
このシート２枚をニッケルネットの両側から圧着して一
体化し、圧さ０．８ ｍｍの水素極用の電極体とした。These two sheets were pressed together from both sides of the nickel net to form an electrode body for a hydrogen electrode with a pressure of 0.8 mm.
一方、正極としては、ニッケル焼結体に活物質を含浸し
たＮｉ００Ｈ［極を使用した。七）くレータとしでは厚
さ０．３ ｍｍのポリアミドの不織布を使用し、電解液
は８ Ｍｏ １３ ／ Ａ！のＫＯＨ容液全便用した。On the other hand, as a positive electrode, a Ni00H electrode made of a nickel sintered body impregnated with an active material was used. 7) A polyamide nonwoven fabric with a thickness of 0.3 mm is used as the filter, and the electrolyte is 8 Mo 13 / A! KOH solution was used for all stools.
第１図は」１記の構成要素を電池に糾んだものである。FIG. 1 shows a battery in which the components listed in ``1'' are assembled.
１は負極、２はセパレータ、３け正極である。４および
５はそれぞれ負極および正極の端子であり、ステンレス
製容器６とは電気的に独立している。なお容器６け、電
池構成要素を組み込んだ後容接して密閉化している。寸
た７は内圧を測定するためのパイプで、８は圧力測定器
である。1 is a negative electrode, 2 is a separator, and 3 is a positive electrode. 4 and 5 are negative and positive electrode terminals, respectively, and are electrically independent from the stainless steel container 6. The six containers were sealed and sealed after the battery components were assembled. Dimension 7 is a pipe for measuring internal pressure, and 8 is a pressure measuring device.
正極３はセパレータ２でＵ字につつみ、その両側から本
発明による負極１を接して配置し、アクリル族のホルダ
ー９で密着させた。１０は電解液である。正極の容量は
１． ＯＡｈ 、負極のＭｍＮ ｉ ４２Ｍｎｏ８は２
． ＯＡｈ分のＨ２を吸収する量が充てんされている。The positive electrode 3 was wrapped in a U-shape with a separator 2, and the negative electrode 1 according to the present invention was placed in contact with both sides of the positive electrode 3, and was brought into close contact with an acrylic holder 9. 10 is an electrolytic solution. The capacity of the positive electrode is 1. OAh, negative electrode MmN i 42Mno8 is 2
．． It is filled with an amount that absorbs H2 equivalent to OAh.
とノｉｌｌヲ、最初ｌ ａｔｍ （Ｏｋｇ／ ｃｍ２）
の状態にした後、２００ｍＡｈで５時間充電し、同じく
２００ｍＡで１．ＯＶｔで放電する（これを１サイクル
とする）ようにして４サイクル繰りかえし、５サイクル
の充電でやめた場合の圧力変化を第２図Ａに示す。また
その後２４時間経過した後５へ目の放′醒を行なった場
合の圧力変化と放電曲線を第３図ＢおよびＤに示す。比
較のだめに水素吸蔵金属としてＬａＮｉ５を使用し、霜
１池作成方法は本実施例と全く間様にして、測定方法も
同一にした結果をそれぞれ＠２図ａ 、 第３図す、ｄ
に示す。なお、湯度はいずれも２５℃である。And no ill, first l atm (Okg/cm2)
After charging at 200mAh for 5 hours, the battery was charged at 200mAh for 1. FIG. 2A shows the pressure change when discharging at OVt (this is considered as one cycle) is repeated for 4 cycles, and charging is stopped after 5 cycles. Further, pressure changes and discharge curves are shown in FIGS. 3B and 3D when the eyes were awakened 24 hours later. For comparison, LaNi5 was used as the hydrogen storage metal, the frost 1 pond creation method was completely different from this example, and the measurement method was also the same.The results are shown in Figure 2a, Figure 3, and d, respectively.
Shown below. In addition, the hot water temperature was 25°C in all cases.
第２図かられかるように、ＬａＮｉ５では充・酷１のた
びに電池内田力がその平惧５プラトー圧に向って−に昇
するのに対して、ＭｍＮｉｔ２’Ｍｎｏ、ｓではほとん
ど上昇しない。寸だ第３図に示すように、２４時間放ｉ
６すると、ＬａＮ＋ ｓによる水素極の電池では電池内
圧が上昇し、しかも放′酷７時間が旬かくなり、明らか
に自己放電しているのに対し、ＭｍＮｉ １Ｍｎ０．１
１ Ｋよる水素極の電池では圧力上昇も、自己放・（５
）もほとんどないことがわかる。As can be seen from FIG. 2, in LaNi5, the battery Uchida force rises to - towards its average plateau pressure every time it is charged or broken, whereas in MmNit2'Mno,s it hardly rises. As shown in Figure 3, 24-hour radio
6, the internal pressure of the battery with a hydrogen electrode using LaN+s increased, and the 7 hours of exposure to the battery increased, clearly self-discharging occurred, whereas the battery with MmNi 1Mn0.1
In batteries with hydrogen electrodes at 1 K, the pressure rise is also caused by self-emission (5
) is also found to be almost non-existent.
以上の説明で明らかなように、本発明によれば、安全で
しかも自己放電の極めて少ない金属酸化物・水素電池を
得ることができる。As is clear from the above description, according to the present invention, it is possible to obtain a metal oxide/hydrogen battery that is safe and has extremely low self-discharge.
第１図は本発明に係わる金属酸化物・水素電池の構造図
、第２図は５ザイクル充電までの電池内圧の変化を示す
曲線図、第３図は５サイクル充電終了後２４時間放置し
たときの電池内圧変化とその後の放電曲線図。
１・・・水素負極、２・・・セパレータ、３・・・金属
酸化物正極、４．５・・・端子、６・・・電池容器、７
・・・圧力測定用パイプ、８・・・圧力計、１０・・・
電解液。Figure 1 is a structural diagram of the metal oxide/hydrogen battery according to the present invention, Figure 2 is a curve diagram showing changes in battery internal pressure up to 5 cycles of charging, and Figure 3 is when left for 24 hours after 5 cycles of charging. Fig. 2 is a diagram showing changes in battery internal pressure and subsequent discharge curves. DESCRIPTION OF SYMBOLS 1... Hydrogen negative electrode, 2... Separator, 3... Metal oxide positive electrode, 4.5... Terminal, 6... Battery container, 7
...Pipe for pressure measurement, 8...Pressure gauge, 10...
Electrolyte.
Claims (1)
分とし水素を活物質とする負極と、アルカリ性の電解液
と、該正極および該負極を分離するセパレータからなる
金属酸化物・水素電池において、前記水素吸蔵金属とし
て２０°Ｃにおける平衡プラトー圧力がｌａｔｍ以下の
ものを用いた事を特徴とする金属酸化物・水素電池。A metal oxide/hydrogen battery consisting of a positive electrode containing a metal oxide as an active material, a negative electrode containing a hydrogen storage alloy as a main component and hydrogen as an active material, an alkaline electrolyte, and a separator that separates the positive electrode and the negative electrode. A metal oxide/hydrogen battery characterized in that the hydrogen storage metal has an equilibrium plateau pressure of latm or less at 20°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58053757A JPS59181459A (en) | 1983-03-31 | 1983-03-31 | Metal oxide hydrogen battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58053757A JPS59181459A (en) | 1983-03-31 | 1983-03-31 | Metal oxide hydrogen battery |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6282430A Division JP3025770B2 (en) | 1994-10-24 | 1994-10-24 | Metal oxide / hydrogen battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59181459A true JPS59181459A (en) | 1984-10-15 |
| JPH0582024B2 JPH0582024B2 (en) | 1993-11-17 |
Family
ID=12951684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58053757A Granted JPS59181459A (en) | 1983-03-31 | 1983-03-31 | Metal oxide hydrogen battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59181459A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6119059A (en) * | 1984-07-04 | 1986-01-27 | Sanyo Electric Co Ltd | Hydrogen occlusion electrode |
| JPS6119060A (en) * | 1984-07-04 | 1986-01-27 | Sanyo Electric Co Ltd | Hydrogen occlusion electrode |
| JPS61168871A (en) * | 1985-01-19 | 1986-07-30 | Sanyo Electric Co Ltd | Hydrogen occlusion electrode |
| JPS6273564A (en) * | 1985-09-26 | 1987-04-04 | Toshiba Corp | Metal oxide-hydrogen battery |
| JPS6280961A (en) * | 1985-10-01 | 1987-04-14 | Matsushita Electric Ind Co Ltd | Alkaline storage battery |
| JPS6280962A (en) * | 1985-10-01 | 1987-04-14 | Matsushita Electric Ind Co Ltd | Alkaline storage battery |
| JPS63131467A (en) * | 1986-11-19 | 1988-06-03 | Sanyo Electric Co Ltd | Metal-hydrogen alkaline storage battery |
| US4837119A (en) * | 1986-12-08 | 1989-06-06 | Matsushita Electric Industrial Co., Ltd. | Sealed storage battery and method for making its electrode |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5145234A (en) * | 1974-08-19 | 1976-04-17 | Philips Nv | |
| JPS53103910A (en) * | 1977-02-23 | 1978-09-09 | Matsushita Electric Ind Co Ltd | Production of hydrogen occluded electrode |
| JPS53111439A (en) * | 1977-03-03 | 1978-09-29 | Philips Nv | Rechargeable electrochemical battery enclosed from outer atmosphere and method of manufacturing same |
| JPS5416632A (en) * | 1977-07-07 | 1979-02-07 | Matsushita Electric Ind Co Ltd | Method of making hydrogen occlusion electrode |
| GB2003927A (en) * | 1977-08-02 | 1979-03-21 | Anvar | Lanthanum and nickel based alloys their manufacture and their electrochemical applications |
| US4214043A (en) * | 1978-02-03 | 1980-07-22 | U.S. Philips Corporation | Rechargeable electrochemical cell |
-
1983
- 1983-03-31 JP JP58053757A patent/JPS59181459A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5145234A (en) * | 1974-08-19 | 1976-04-17 | Philips Nv | |
| JPS53103910A (en) * | 1977-02-23 | 1978-09-09 | Matsushita Electric Ind Co Ltd | Production of hydrogen occluded electrode |
| JPS53111439A (en) * | 1977-03-03 | 1978-09-29 | Philips Nv | Rechargeable electrochemical battery enclosed from outer atmosphere and method of manufacturing same |
| JPS5416632A (en) * | 1977-07-07 | 1979-02-07 | Matsushita Electric Ind Co Ltd | Method of making hydrogen occlusion electrode |
| GB2003927A (en) * | 1977-08-02 | 1979-03-21 | Anvar | Lanthanum and nickel based alloys their manufacture and their electrochemical applications |
| US4214043A (en) * | 1978-02-03 | 1980-07-22 | U.S. Philips Corporation | Rechargeable electrochemical cell |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6119059A (en) * | 1984-07-04 | 1986-01-27 | Sanyo Electric Co Ltd | Hydrogen occlusion electrode |
| JPS6119060A (en) * | 1984-07-04 | 1986-01-27 | Sanyo Electric Co Ltd | Hydrogen occlusion electrode |
| JPS61168871A (en) * | 1985-01-19 | 1986-07-30 | Sanyo Electric Co Ltd | Hydrogen occlusion electrode |
| JPH0586622B2 (en) * | 1985-01-19 | 1993-12-13 | Sanyo Electric Co | |
| JPS6273564A (en) * | 1985-09-26 | 1987-04-04 | Toshiba Corp | Metal oxide-hydrogen battery |
| JP2566912B2 (en) * | 1985-09-26 | 1996-12-25 | 株式会社東芝 | Nickel oxide / hydrogen battery |
| JPS6280961A (en) * | 1985-10-01 | 1987-04-14 | Matsushita Electric Ind Co Ltd | Alkaline storage battery |
| JPS6280962A (en) * | 1985-10-01 | 1987-04-14 | Matsushita Electric Ind Co Ltd | Alkaline storage battery |
| JPH0642367B2 (en) * | 1985-10-01 | 1994-06-01 | 松下電器産業株式会社 | Alkaline storage battery |
| JPH0642368B2 (en) * | 1985-10-01 | 1994-06-01 | 松下電器産業株式会社 | Alkaline storage battery |
| JPS63131467A (en) * | 1986-11-19 | 1988-06-03 | Sanyo Electric Co Ltd | Metal-hydrogen alkaline storage battery |
| US4837119A (en) * | 1986-12-08 | 1989-06-06 | Matsushita Electric Industrial Co., Ltd. | Sealed storage battery and method for making its electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0582024B2 (en) | 1993-11-17 |
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