JP4494566B2 - Negative electrode active material for alkaline secondary battery and method for producing the same - Google Patents
Negative electrode active material for alkaline secondary battery and method for producing the same Download PDFInfo
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- JP4494566B2 JP4494566B2 JP35407999A JP35407999A JP4494566B2 JP 4494566 B2 JP4494566 B2 JP 4494566B2 JP 35407999 A JP35407999 A JP 35407999A JP 35407999 A JP35407999 A JP 35407999A JP 4494566 B2 JP4494566 B2 JP 4494566B2
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Description
【０００１】
【発明の属する技術分野】
本発明は、高容量でサイクル寿命に優れたアルカリ２次電池を提供することができるアルカリ２次電池用負極活物質、その製造方法及び該負極活物質を備えたアルカリ２次電池に関する。
【０００２】
【従来の技術】
近年、ニッケル−カドミウム２次電池に代わる高容量の電池として、希土類金属−ニッケル合金をはじめとする水素吸蔵合金を負極活物質とする金属水素化物２次電池(以下ＭＨ電池という)が注目されている。ＭＨ電池では、充放電サイクルの繰返しにより、負極を構成する水素吸蔵合金又は水素化物が酸化されて性能が劣化するという問題がある。この問題を解決するために、例えば、希土類酸化物等の化合物を負極など電池内部に添加することによって、前記性能の劣化を抑制しようという試みがなされている(特開平６−２１５７６５号公報、特開平８−２２２２１０号公報、特開平８−３２９９３４号公報、特開平１０−１０６５５０号公報等）。
しかし、上述のような方法では、負極活物質中に水素吸蔵能力を示さない添加物を混合することになるため、負極活物質の単位質量当たりの容量が低下するという問題がある。
【０００３】
【発明が解決しようとする課題】
従って、本発明の目的は、電池容量の低下と水素吸蔵合金の劣化とを抑制することができる、高容量でサイクル寿命に優れたアルカリ２次電池が提供できる負極活物質及びその製造方法を提供することにある。
本発明の別の目的は、高容量でサイクル寿命に優れたアルカリ２次電池を提供することにある。
【０００４】
【課題を解決するための手段】
本発明によれば、水素吸蔵合金とプロトン伝導性複合酸化物とを含み、該プロトン伝導性複合酸化物が、ＡＢ 1-X Ｍ X Ｏ 3- α(ＡはＣａ、Ｓｒ、Ｂａ及びこれらの混合物からなる群より選択される１種又は２種以上を示し、ＢはＣｅを示し、Ｍは希土類元素を示す。ただしＢ≠Ｍである。Ｘは、０＜Ｘ≦０．５であり、αは酸素欠損量を示す。）で表されることを特徴とするアルカリ２次電池用負極活物質が提供される。
また本発明によれば、水素吸蔵合金とプロトン伝導性複合酸化物を混合した後、メカニカルミリングを行うことを特徴とする上記アルカリ２次電池用負極活物質の製造方法が提供される。
【０００５】
【発明の実施の形態】
以下、本発明をさらに詳細に説明する。
本発明のアルカリ２次電池用負極活物質(以下、本発明の負極活物質と略すことがある)は、水素吸蔵合金を主成分とする負極活物質が、プロトン伝導性複合酸化物を含むことを特徴とする。
前記水素吸蔵合金としては、アルカリ２次電池の負極に使用しうる組成であれば特に限定されず、例えば、ＡＢ5型、ＡＢ2型、ＡＢ型、Ａ2Ｂ型等の水素吸蔵合金を適宜選択して使用することができる。
【０００６】
前記プロトン伝導性複合酸化物は、ＡＢ1-XＭXＯ3-α(ＡはＣａ、Ｓｒ、Ｂａ及びこれらの混合物からなる群より選択される１種又は２種以上を示し、ＢはＣｅを示し、Ｍは希土類元素を示す。ただしＢ≠Ｍである。Ｘは、０＜Ｘ≦０．５であり、αは酸素欠損量を示す。)で表され、プロトン伝導性を示すものであれば特に限定されない。好ましくは、ＳｒＣｅＹｂＯ系、ＢａＣｅＹＯ系やＢａＣｅＧｄＯ系のプロトン伝導性複合酸化物等が挙げられる。上記式中のＸは、Ｂ元素をＭ元素で置換する際の置換量に当たるが、Ｘは０＜Ｘ≦０．５、好ましくは０＜Ｘ≦０．３、さらに好ましくは０＜Ｘ≦０．１である。Ｘが０．５を超える場合にはプロトン伝導性が低下するため好ましくない。
プロトン伝導性複合酸化物を調製するには、公知の方法で行なうことができ、例えば、上記式で示される組成に調製した酸化物原料粉末を、所望形状に成形し、焼成した後粉砕する方法等により得ることができる。
【０００７】
本発明の負極活物質において、プロトン伝導性複合酸化物の含有割合は、水素吸蔵合金及びプロトン伝導性複合酸化物の合計量に対して０．１質量％以上が好ましい。含有割合が０．１質量％未満では、添加の効果が得られ難く、また１０質量％を超えると容量が低下する恐れがあるので０．１〜１０質量％が好ましく、さらに好ましくは０．１〜５質量％である。
本発明の負極活物質は、通常、水素吸蔵合金表面にプロトン伝導性複合酸化物が付着した状態であれば所望の効果を得ることができるが、さらなる効果の向上を望む場合は、プロトン伝導性複合酸化物が水素吸蔵合金表面に一部埋没した状態が好ましく、更にはプロトン伝導性複合酸化物が水素吸蔵合金表面において傾斜材料的に複合化された状態であることが望ましい。このような状態の確認は、例えば、ＴＥＭ、ＥＳＣＡ、ＸＲＤ等により行うことができる。
【０００８】
本発明の負極活物質の製造方法では、水素吸蔵合金とプロトン伝導性複合酸化物とを混合した後、メカニカルミリングを行うことを特徴とする。
本発明の製造方法に用いるプロトン伝導性複合酸化物は、上記組成を有するプロトン伝導性複合酸化物であって、好ましくは、比表面積の大きなものがよい。好ましい比表面積としては、１ｍ2／ｇ以上、より好ましくは５ｍ2／ｇ以上である。これらの比表面積を得る手段としては、プロトン伝導性複合酸化物調製時の粉砕をメカニカルミリングにより行う方法等が１例として挙げられる。
【０００９】
本発明の製造方法において、水素吸蔵合金とプロトン伝導性複合酸化物との混合割合は、得られる負極活物質中のプロトン伝導性複合酸化物の含有割合が、上記配合割合となるように適宜選択して配合することができる。
【００１０】
本発明の製造方法において、水素吸蔵合金とプロトン伝導性複合酸化物との混合物に対してメカニカルミリングを行うには、例えば、遊星ボールを用いた遊星ボールミル等を用いて行うことができる。この際、メカニカルミリングの条件は、水素吸蔵合金とプロトン伝導性複合酸化物が均一に混合されるだけでなく、水素吸蔵合金表面にプロトン伝導性複合酸化物が一様に付着した状態となるような条件を適宜設定して行うことが好ましい。通常、水素吸蔵合金表面にプロトン伝導性複合酸化物が付着した状態であれば所望の効果を得ることができるが、さらなる効果の向上を望む場合は、プロトン伝導性複合酸化物が水素吸蔵合金表面に一部埋没した状態となる条件を選択することがが好ましい。更にはプロトン伝導性複合酸化物が水素吸蔵合金表面において傾斜材料的に複合化される条件を選択することが望ましい。
【００１１】
メカニカルミリングを行う際の雰囲気は特に限定されないが、得られる合金の酸化防止や表面修飾を目的として、希ガス、水蒸気、酸素、窒素、水素、二酸化炭素又はこれらの混合物等の雰囲気が好ましい。
【００１２】
本発明のアルカリ２次電池は、負極に本発明の負極活物質を含んでおれば良く、他の構成は、公知の構成等を適宜組合せたもので良く、特に限定されない。負極材料の調製も、例えば、通常用いる導電助剤や結着剤を用いて公知の方法等により行うことができる。
【００１３】
【発明の効果】
本発明のアルカリ２次電池用負極活物質は、水素吸蔵合金を主成分とする負極活物質がプロトン伝導性複合酸化物を含むので、アルカリ２次電池用負極に用いることによって電池容量及びサイクル寿命を向上させることができ、これを用いたアルカリ２次電池は、サイクル寿命に優れると共に、高い電池容量が維持される。また、本発明の製造方法では、このような負極活物質を容易に得ることができる。
【００１４】
【実施例】
以下、本発明を実施例及び比較例により更に詳細に説明するが、本発明はこれらに限定されるものではない。
合成例１（プロトン伝導性複合酸化物の合成）
ＳｒＣＯ3、ＣｅＯ2、Ｙｂ2Ｏ3をモル比で１：０．９５：０．０５となるように混合し、ペレット状に成形した後１４００℃で２０時間焼成した。得られたペレットを乳鉢で粉砕し再び成形し１５３０℃で１０時間焼成後、乳鉢で粉砕してＳｒＣｅ0.95Ｙｂ0.05Ｏ3粉末を得た。得られた複合酸化物をステンレスボールと共にステンレスのポットに入れ、遊星ボールミル中で１０時間ボールミリングを行った。これを酸化物Ａとする。
ＢａＣＯ3、ＣｅＯ2、Ｙ2Ｏ3をモル比で１：０．９０：０．０５となるように混合し、ペレット状に成形した後１４００℃で２０時間焼成した。得られたペレットを乳鉢で粉砕し再び成形し１５３０℃で１０時間焼成後、乳鉢で紛砕して、ＢａＣｅ0.90Ｙ0.05Ｏ3粉末を得た。得られた複合酸化物をステンレスボールと共にステンレスのポットに入れ、遊星ボールミル中で１０時間ボールミリングを行った。これを酸化物Ｂとする。
酸化物Ａ及びＢについて、ＩＣＰ発光分光分析装置により組成分析、X線回折の測定を行い組成式どおりの化合物であることを確認した。また、ＢＥＴ法により比表面積を測定したところ、酸化物Ａは５．３ｍ2／ｇ、酸化物Ｂは５．８ｍ2／ｇであった。更に、これらの１０００℃におけるプロトン伝導率を測定したところ、酸化物Ａは１．８×１０-2Ｓ／ｃｍ2、酸化物Ｂは２．０×１０-2Ｓ／ｃｍ2であった。
【００１５】
合成例２（水素吸蔵合金の作成）
ミッシュメタル、ニッケル、コバルト、アルミニウム、マンガンを元素比で１：３．４：０．８：０．２：０．６となるように混合し高周波溶解炉で溶解した。次いで、溶解物を金型に鋳込んで水素吸蔵合金を作製した。水素吸蔵合金を乳鉢にて粉砕し、水素吸蔵合金粉未を得た。
【００１６】
実施例１
合成例１で調製した酸化物Ａ ５ｇと、合成例２で調製した水素吸蔵合金４９５ｇとをステンレスボールと共にステンレスのポットに入れ、遊星ボールミル中で２０時間ボールミリングを行い、負極活物質を得た。得られた負極活物質は、ＴＥＭにより測定したところ、水素吸蔵合金と酸化物Ａとが傾斜機能材料的に接合していることが確認された。ここで、傾斜機能材料的とは、接合部位に、水素吸蔵合金からなる層と、水素吸蔵合金及び酸化物Ａが入り混じった層と、酸化物Ａからなる層とが段階的に観察されることを言う。
次いで、得られた負極活物質２ｇに導電助剤としてニッケル粉末２ｇ、結着剤としてＰＴＦＥ０．２ｇを添加し、乳鉢で混合することにより負極を作成した。得られた負極と、セパレータとしてのポリプロピレン不織布と、正極としての水酸化ニッケルと、電解液としての６Ｎの水酸化カリウムとを用いて電池を作成した。作成した電池について負極容量と、５００サイクルにおける容量維持率とを測定した。結果を表１に示す。
【００１７】
実施例２
酸化物Ａの代わりに酸化物Ｂを用いた他は実施例１と同様の操作を行い負極活物質及び電池を得、各測定を行った。結果を表１に示す。
【００１８】
比較例１
酸化物を用いず、合成例２で調製した水素吸蔵合金を５００ｇ用いた他は実施例１と同様の操作を行い電池を得、各測定を行った。結果を表１に示す。
【００１９】
比較例２
酸化物Ａの代わりに酸化イットリウムを用いた他は実施例１と同様の操作を行い電池を得、各測定を行った。結果を表１に示す。
【００２０】
【表１】
BACKGROUND OF THE INVENTION
The present invention relates to a negative electrode active material for an alkaline secondary battery capable of providing an alkaline secondary battery having a high capacity and excellent cycle life, a method for producing the same, and an alkaline secondary battery including the negative electrode active material.
[0002]
[Prior art]
In recent years, metal hydride secondary batteries (hereinafter referred to as MH batteries) using a hydrogen storage alloy such as a rare earth metal-nickel alloy as a negative electrode active material have attracted attention as high-capacity batteries replacing nickel-cadmium secondary batteries. Yes. In the MH battery, there is a problem that the performance is deteriorated due to oxidation of the hydrogen storage alloy or hydride constituting the negative electrode due to repeated charge and discharge cycles. In order to solve this problem, for example, an attempt has been made to suppress the deterioration of the performance by adding a compound such as a rare earth oxide to the inside of the battery, such as a negative electrode (Japanese Patent Laid-Open No. Hei 6-215765, Japanese Patent Application Laid-Open No. 6-215765). (Kaihei 8-222210, JP-A-8-329934, JP-A-10-106550, etc.).
However, the method as described above has a problem in that the capacity per unit mass of the negative electrode active material is reduced because an additive that does not exhibit hydrogen storage capacity is mixed in the negative electrode active material.
[0003]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a negative electrode active material capable of suppressing a decrease in battery capacity and deterioration of a hydrogen storage alloy and capable of providing an alkaline secondary battery having a high capacity and excellent cycle life, and a method for producing the same. There is to do.
Another object of the present invention is to provide an alkaline secondary battery having high capacity and excellent cycle life.
[0004]
[Means for Solving the Problems]
According to the present invention, seen containing a hydrogen storage alloy and a proton-conductive composite oxide, said proton-conductive composite oxide, AB 1-X M X O 3- α (A is Ca, Sr, Ba and their 1 or 2 or more selected from the group consisting of a mixture of the following: B represents Ce, M represents a rare earth element, B ≠ M, X is 0 <X ≦ 0.5 , Α represents an oxygen deficiency amount), and a negative electrode active material for an alkaline secondary battery is provided.
Moreover, according to this invention, after mixing a hydrogen storage alloy and a proton conductive composite oxide, the manufacturing method of the said negative electrode active material for alkaline secondary batteries characterized by performing mechanical milling is provided.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
The negative electrode active material for an alkaline secondary battery of the present invention (hereinafter may be abbreviated as the negative electrode active material of the present invention) is that the negative electrode active material mainly composed of a hydrogen storage alloy contains a proton conductive composite oxide. It is characterized by.
The hydrogen storage alloy is not particularly limited as long as it is a composition that can be used for a negative electrode of an alkaline secondary battery. For example, a hydrogen storage alloy such as AB 5 type, AB 2 type, AB type, A 2 B type or the like is appropriately used. You can select and use.
[0006]
The proton-conductive composite oxide is AB 1-X M X O 3- α (A is one or more selected from the group consisting of Ca, Sr, Ba and mixtures thereof, and B is Ce are shown, M is. However B ≠ M showing a dilute Doruimoto iodine. X is 0 <X ≦ 0.5, alpha is expressed amount of oxygen vacancies in the shown to.), proton conductivity If it shows, it will not specifically limit. Preferably, SrCeYbO-based, BaCeYO-based, BaCeGdO-based proton conductive composite oxides, and the like can be used. X in the above formula corresponds to the substitution amount when the B element is substituted with the M element. X is 0 < X ≦ 0.5, preferably 0 < X ≦ 0.3, more preferably 0 < X ≦ 0. .1. When X exceeds 0.5, proton conductivity is lowered, which is not preferable.
The proton conductive composite oxide can be prepared by a known method. For example, the oxide raw material powder prepared in the composition represented by the above formula is formed into a desired shape, baked and then pulverized. Etc. can be obtained.
[0007]
In the negative electrode active material of the present invention, the content ratio of the proton conductive composite oxide is preferably 0.1% by mass or more with respect to the total amount of the hydrogen storage alloy and the proton conductive composite oxide. If the content is less than 0.1% by mass, the effect of addition is difficult to obtain, and if it exceeds 10% by mass, the capacity may decrease, so 0.1 to 10% by mass is preferable, and more preferably 0.1% by mass. ˜5 mass%.
The negative electrode active material of the present invention can usually obtain a desired effect as long as the proton conductive composite oxide is attached to the surface of the hydrogen storage alloy, but if further improvement of the effect is desired, the proton conductivity can be obtained. A state in which the composite oxide is partially buried in the surface of the hydrogen storage alloy is preferable, and further, it is desirable that the proton conductive composite oxide is in a state of being compounded as a gradient material on the surface of the hydrogen storage alloy. Such confirmation of the state can be performed by, for example, TEM, ESCA, XRD, or the like.
[0008]
In the method for producing a negative electrode active material of the present invention, mechanical milling is performed after mixing a hydrogen storage alloy and a proton conductive composite oxide.
The proton conductive composite oxide used in the production method of the present invention is a proton conductive composite oxide having the above composition, and preferably has a large specific surface area. The specific surface area is preferably 1 m 2 / g or more, more preferably 5 m 2 / g or more. Examples of means for obtaining these specific surface areas include a method in which pulverization at the time of preparing the proton conductive composite oxide is performed by mechanical milling.
[0009]
In the production method of the present invention, the mixing ratio of the hydrogen storage alloy and the proton conductive composite oxide is appropriately selected so that the content ratio of the proton conductive composite oxide in the obtained negative electrode active material becomes the above blending ratio. Can be blended.
[0010]
In the production method of the present invention, mechanical milling can be performed on a mixture of a hydrogen storage alloy and a proton conductive composite oxide using, for example, a planetary ball mill using a planetary ball. At this time, the mechanical milling conditions are such that not only the hydrogen storage alloy and the proton conductive composite oxide are uniformly mixed, but also the proton conductive composite oxide is uniformly attached to the surface of the hydrogen storage alloy. It is preferable to carry out by appropriately setting various conditions. Usually, the desired effect can be obtained as long as the proton conductive composite oxide is attached to the surface of the hydrogen storage alloy. However, when further improvement of the effect is desired, the proton conductive composite oxide is used on the surface of the hydrogen storage alloy. It is preferable to select a condition that results in a partially buried state. Furthermore, it is desirable to select conditions under which the proton conductive composite oxide is compounded like a gradient material on the surface of the hydrogen storage alloy.
[0011]
Although the atmosphere at the time of performing mechanical milling is not particularly limited, an atmosphere of a rare gas, water vapor, oxygen, nitrogen, hydrogen, carbon dioxide, or a mixture thereof is preferable for the purpose of preventing oxidation and surface modification of the obtained alloy.
[0012]
The alkaline secondary battery of the present invention only needs to contain the negative electrode active material of the present invention in the negative electrode, and other configurations may be appropriately combined with known configurations and the like, and are not particularly limited. The negative electrode material can also be prepared, for example, by a known method or the like using a commonly used conductive additive or binder.
[0013]
【The invention's effect】
In the negative electrode active material for alkaline secondary batteries of the present invention, since the negative electrode active material mainly composed of a hydrogen storage alloy contains a proton conductive composite oxide, battery capacity and cycle life can be obtained by using the negative electrode active material for alkaline secondary batteries. The alkaline secondary battery using the same has excellent cycle life and maintains a high battery capacity. Moreover, in the manufacturing method of this invention, such a negative electrode active material can be obtained easily.
[0014]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these.
Synthesis Example 1 ( Synthesis of proton conductive composite oxide)
SrCO 3 , CeO 2 and Yb 2 O 3 were mixed at a molar ratio of 1: 0.95: 0.05, formed into a pellet, and then fired at 1400 ° C. for 20 hours. The obtained pellets were pulverized in a mortar and molded again, baked at 1530 ° C. for 10 hours, and then pulverized in a mortar to obtain SrCe 0.95 Yb 0.05 O 3 powder. The obtained composite oxide was put into a stainless steel pot together with a stainless ball, and ball milling was performed in a planetary ball mill for 10 hours. This is oxide A.
BaCO 3 , CeO 2 , and Y 2 O 3 were mixed at a molar ratio of 1: 0.90: 0.05, formed into a pellet, and then fired at 1400 ° C. for 20 hours. The obtained pellets were pulverized in a mortar and molded again, fired at 1530 ° C. for 10 hours, and then pulverized in a mortar to obtain BaCe 0.90 Y 0.05 O 3 powder. The obtained composite oxide was put into a stainless steel pot together with a stainless ball, and ball milling was performed in a planetary ball mill for 10 hours. This is oxide B.
About oxide A and B, the composition analysis and the X-ray-diffraction measurement were performed with the ICP emission-spectral-analysis apparatus, and it confirmed that it was a compound according to a composition formula. Further, when the specific surface area was measured by the BET method, the oxide A was 5.3 m 2 / g, and the oxide B was 5.8 m 2 / g. Furthermore, when the proton conductivity at 1000 ° C. was measured, the oxide A was 1.8 × 10 −2 S / cm 2 , and the oxide B was 2.0 × 10 −2 S / cm 2 .
[0015]
Synthesis example 2 ( Preparation of hydrogen storage alloy)
Misch metal, nickel, cobalt, aluminum, and manganese were mixed at an element ratio of 1: 3.4: 0.8: 0.2: 0.6 and dissolved in a high-frequency melting furnace. Next, the melt was cast into a mold to produce a hydrogen storage alloy. The hydrogen storage alloy was pulverized in a mortar to obtain no hydrogen storage alloy powder.
[0016]
Example 1
5 g of oxide A prepared in Synthesis Example 1 and 495 g of the hydrogen storage alloy prepared in Synthesis Example 2 were placed in a stainless steel pot together with a stainless steel ball, and ball milling was performed in a planetary ball mill for 20 hours to obtain a negative electrode active material. . When the obtained negative electrode active material was measured by TEM, it was confirmed that the hydrogen storage alloy and the oxide A were joined in a functionally gradient material. Here, in terms of functionally graded material, a layer made of a hydrogen storage alloy, a layer mixed with the hydrogen storage alloy and the oxide A, and a layer made of the oxide A are observed in stages at the bonding site. Say that.
Next, 2 g of nickel powder as a conductive additive and 0.2 g of PTFE as a binder were added to 2 g of the obtained negative electrode active material, and mixed in a mortar to prepare a negative electrode. A battery was prepared using the obtained negative electrode, a polypropylene nonwoven fabric as a separator, nickel hydroxide as a positive electrode, and 6N potassium hydroxide as an electrolytic solution. The produced battery was measured for negative electrode capacity and capacity retention rate at 500 cycles. The results are shown in Table 1.
[0017]
Example 2
A negative electrode active material and a battery were obtained in the same manner as in Example 1 except that oxide B was used instead of oxide A, and each measurement was performed. The results are shown in Table 1.
[0018]
Comparative Example 1
A battery was obtained by performing the same operation as in Example 1 except that 500 g of the hydrogen storage alloy prepared in Synthesis Example 2 was used without using an oxide, and each measurement was performed. The results are shown in Table 1.
[0019]
Comparative Example 2
A battery was obtained in the same manner as in Example 1 except that yttrium oxide was used instead of oxide A, and each measurement was performed. The results are shown in Table 1.
[0020]
[Table 1]
Claims (5)
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| JPS62296365A (en) * | 1986-06-16 | 1987-12-23 | Matsushita Electric Ind Co Ltd | Sealed alkaline storage battery |
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| JP3326197B2 (en) * | 1992-06-10 | 2002-09-17 | 三洋電機株式会社 | Hydrogen storage alloy electrode and method for producing the same |
| JPH0829376A (en) * | 1994-07-12 | 1996-02-02 | Tokyo Yogyo Co Ltd | Sensor for measuring quantity of hydrogen dissolved in molten metal |
| JPH0952764A (en) * | 1995-08-17 | 1997-02-25 | Toyota Central Res & Dev Lab Inc | Multiple oxide sintered compact and its manufacture |
| JP3927663B2 (en) * | 1997-10-15 | 2007-06-13 | 松下電器産業株式会社 | Mixed ion conductor |
| JPH11204112A (en) * | 1998-01-12 | 1999-07-30 | Furukawa Battery Co Ltd:The | Nickel hydrogen battery |
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