JP4365470B2 - Beta-alumina tube for sodium-sulfur battery and method for producing the same - Google Patents
Beta-alumina tube for sodium-sulfur battery and method for producing the same Download PDFInfo
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- JP4365470B2 JP4365470B2 JP05212799A JP5212799A JP4365470B2 JP 4365470 B2 JP4365470 B2 JP 4365470B2 JP 05212799 A JP05212799 A JP 05212799A JP 5212799 A JP5212799 A JP 5212799A JP 4365470 B2 JP4365470 B2 JP 4365470B2
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- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 title claims description 58
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 34
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- 229910052596 spinel Inorganic materials 0.000 claims description 16
- 239000011029 spinel Substances 0.000 claims description 16
- 239000000395 magnesium oxide Substances 0.000 claims description 15
- 238000010304 firing Methods 0.000 claims description 7
- 239000007784 solid electrolyte Substances 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 description 24
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 23
- 238000000034 method Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000008646 thermal stress Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 208000032953 Device battery issue Diseases 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
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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
- 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
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- Compositions Of Oxide Ceramics (AREA)
- Secondary Cells (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、ナトリウム−硫黄電池の固体電解質管に用いる有底円筒状ベ−タアルミナ管に関するものである。
【０００２】
【従来の技術】
ベータアルミナセラミックスは優れたナトリウムイオン伝導性を利用して、ナトリウム−硫黄電池用固体電解質として研究開発が進められている。ナトリウム−硫黄電池においてベータアルミナセラミックスは、電池の正極室と負極室との隔壁の役割も果たしている。隔壁の破損が起こると両活物質が爆発的に反応を起こし危険であるため、ベータアルミナセラミックスには高い機械的強度も要求される。
【０００３】
機械的強度向上のためには、ベータアルミナと反応しない高純度のジルコニア微粒子を分散させてセラミックスを複合強化する方法（米国特許第４３５８５１６号）が提案されている。また、ホットプレスで予備焼結を行い焼結密度を高める方法（特開昭４９−３０４０７号公報）、ベータアルミナ製造工程の各段階において、１００〜２００μｍの粗粒原料粉末を除去する方法（特開平２−１５５７６号公報）などが提案されている。
【０００４】
【発明が解決しようとする課題】
これらセラミックスの強度を向上する試みは、電池組み立て時のベータアルミナセラミックス破損を低減する効果はあるが、電池運転時のベータアルミナセラミックス管破損に対しては、有効ではなかった。
【０００５】
このナトリウム−硫黄電池の運転中に起こる電池破損は、高い電流密度で運転した場合に発生しやすい。具体的には、ベータアルミナ管の有底部と円筒側面部を連結する接続部位における破損がかなりの割合で発生する。破損発生のメカニズムとしては、円筒側面部や有底部と比べて該接続部位は曲率半径が小さいため、該接続部位に電流集中が起きて局所的に温度が高くなり、熱応力によって破損するものと考えられる。
【０００６】
本発明の目的は、ナトリウムイオン伝導特性がよく、高強度で、電池の運転時及び組立時に不具合を生じない信頼性の高いナトリウム−硫黄電池の固体電解質用ベータアルミナ管を提供することを目的とする。特には、ナトリウム−硫黄電池の運転時に発生するベータアルミナ管の破損の低減を目的とする。
【０００７】
【課題を解決するための手段】
本発明は、有底円筒状のベータアルミナ管の有底部と円筒側面部とを連結する接続部分を備え、前記接続部分の少なくとも一部が、マグネシア、スピネル、ジルコニアもしくはアルミナからなる接触部材を接触させた状態にて焼成されてなるものである。本発明の構成部分を図１を例に以下に説明する。ここにいう「有底部」とは、例えば図１中の２をいう。ここにいう「円筒側面部」とは、例えば図１中の３をいう。ここにいう「接続部分」とは、例えば図１中の４をいう。係る構成により、上記接続部分への電流集中を防いで局所的な発熱を低減させることにより、熱応力の発生を低減し、ベータアルミナ管の破損を防止できる。
【０００８】
請求項１の発明は、前記接続部分の少なくとも一部に、マグネシア、スピネル、ジルコニアもしくはアルミナからなる接触部材を接触させた状態にて焼成することにより、前記接続部分の少なくとも一部に、マグネシア、スピネル、ジルコニアもしくはアルミナが生成することを要旨とする。ベータアルミナ管のナトリウムイオン伝導経路を非ナトリウムイオン伝導部材が寸断するため、局部的な電流集中を防ぐことができ、ベータアルミナ管の有底部と円筒側面部との接続部分にかかる熱応力を低減して、ベータアルミナセラミックス破損を防止できる。
【０００９】
本発明のマグネシア、スピネル、ジルコニア、アルミナはナトリウムイオン伝導率が実質的に無い。そのため、係る混合セラミックスがベータアルミナ管のナトリウムイオン伝導経路を寸断して局所的な電流集中を防ぎ、ベータアルミナ管の有底部と円筒側面部との接続部分にかかる熱応力を低減して、ベータアルミナセラミックス破損を防止できる。
【００１０】
請求項２の発明は、非ナトリウムイオン伝導性部材であるマグネシア、スピネル、ジルコニアもしくはアルミナを有底円筒状のベータアルミナ管の有底部と円筒側面部との少なくとも一部を連結する接続部分に接触させた状態で焼成するベータアルミナ管の製造方法を要旨とする。得られるベータアルミナ管の上記接触部分の少なくとも一部に非ナトリウムイオン伝導性部材であるマグネシア、スピネル、ジルコニアもしくはアルミナが生成するため、上記接続部分のナトリウムイオン伝導率が上記接続部分以外のベータアルミナと比較して小さくなる、もしくは実質的に無くなる。その結果、局所的な電流集中を防ぎ、ベータアルミナ管の有底部と円筒側面部との接続部分にかかる熱応力を低減して、ベータアルミナセラミックス破損を防止できる。
【００１１】
請求項３の発明は、非ナトリウムイオン伝導性部材であるマグネシア、スピネル、ジルコニアもしくはアルミナの焼結体を有底円筒状のベータアルミナ管の有底部と円筒側面部との少なくとも一部を連結する接続部分に接触させた状態で焼成するベータアルミナ管の製造方法を要旨とする。本発明の具体例を図２乃至図４に例示する。ベータアルミナ管の成形体１をその有底面を上に向けて立てて、上記の非ナトリウムイオン伝導性部材の焼結体からなる治具５を上記接続部に接するように配置した状態で焼成する方法（図２を参照）や、非ナトリウムイオン伝導性部材の焼結体からなる柱状治具６に成形体１を被せた状態で焼成する方法（図３を参照）や、非ナトリウムイオン伝導性部材の焼結体からなり、成形体１の接続部分３を保持する治具７に成形体１をその有底面を下に向けて立てた状態で焼成する方法（図４を参照）等を挙げることができる。但し、本発明の構成は上記の図２乃至図４に例示された具体的な構成にのみ限定されるものではない。
【００１２】
本発明の具体例を図５に例示する。耐火材８に図５に示すように非ナトリウムイオン伝導性部材の粉末９を配置し、粉末９の上に成形体１の接続部分３を保持するように立てた状態で焼成する方法等を挙げることができる。但し、本発明の構成は上記の図５に例示された具体的な構成にのみ限定されるものではない。
【００１３】
他の具体例としては、請求項３の発明で例示した各種治具（図２乃至図４を参照）を成形体で置き換えた方法を挙げることができる。但し、本発明の構成は上記の図２乃至図４に例示された具体的な構成にのみ限定されるものではない。
【００１４】
以上、請求項２又は３のいずれの製造方法を用いても、得られるベータアルミナ管の上記接触部分の少なくとも一部に非ナトリウムイオン伝導性部材であるマグネシア、スピネル、ジルコニアもしくはアルミナが生成するため、上記接続部分のナトリウムイオン伝導率が上記接続部分以外のベータアルミナと比較して小さくなる、もしくは実質的に無くなる。その結果、局所的な電流集中を防ぎ、ベータアルミナ管の有底部と円筒側面部との接続部分にかかる熱応力を低減して、ベータアルミナセラミックス破損を防止できる。
【００１５】
【実施例】
ベータアルミナセラミックスの作製は、出発原料としてαアルミナ、炭酸ナトリウム、安定化剤として炭酸リチウムを用いた。αアルミナは純度９９．９％の原料、炭酸ナトリウム、炭酸リチウムは試薬１級を用いた。αアルミナ、炭酸ナトリウム、炭酸リチウムをアルミナ、酸化ナトリウム、酸化リチウムの酸化物換算で９０．４％、８．８５％、０．７５％となるように所定量混合し、１２５０℃で１０時間仮焼の後、振動ミルで粉砕し粉砕原料を得た。
【００１６】
該ベータアルミナ粉砕粉末と、イットリア安定化酸化ジルコニウム(ベータアルミナ粉砕粉末１００重量部に対して３重量部）を水溶媒で混合しスラリとし、スプレードライ造粒し造粒粉末を得た。粉末は焼結後に長さ４００ｍｍ×外径４５ｍｍ×肉厚２．５ｍｍとなるようチューブ形状に成形し、所定の温度で１時間保持して焼成を行った。焼成は、表１に示すようなマグネシア、スピネル、ジルコニア、アルミナからなる接触部材をベータアルミナ有底円筒成形体の有底部と円筒側面部を連結する接続部分である曲面部に接触させた状態（図２に示した状態）で焼成した。
【００１７】
このようにして得たベータアルミナ管から切り出した試験片で、エタノールを用いた浮力法により嵩密度を測定し、理論密度との比（相対密度）を算出した。また、ベータアルミナ管形状のまま、Ｎａ-Ｎａセルで４端子法で３５０度におけるナトリウムイオン伝導度（比抵抗値）を測定した。また、ベータアルミナ管の内圧破壊強度を測定した。内圧破壊強度は、ベータアルミナ管の内側全体に圧力を印加し、破壊した時点の強度をベータアルミナ管の形状から計算して求めたものである。各ロットにつき８本のベータアルミナ管で内圧強度を測定し、平均値を求めた。また、上記曲面部の組成は、ベータアルミナ管を切り出し、ＥＤＳ（エネルギー分散型Ｘ線分光）にて元素分析を行った。また、Ｘ線回折により結晶構造を同定した。結果を表１に示す。
【００１８】
さらに同一ロットのベータアルミナ管を用いてナトリウム−硫黄電池を作製し、ナトリウム−硫黄電池としての信頼性を評価する目的で、充放電試験を行った。条件は、３３０℃（電池作動温度）で３時間放電−１時間休止−３時間充電１時間休止の充放電サイクル（通常のロードレベリングの約３倍の急速充放電）を５００回繰り返し、信頼性を評価した。ベータアルミナアルミナの破損に伴う電池不具合が発生すると充放電が不可能になる。各ロットにつき１０セル作製し、５００回の連続充放電試験を行った。各ロットにおいて５００回までの充放電で発生したベータアルミナ割れによる不具合の発生率を調査した。結果を表１に示す。
【００１９】
【表１】
表１の結果より、本発明の実施例である試料番号１乃至試料番号１２では破損率が３０％以下であるのに対して、比較例である試料番号１３では破損率が７０％と劣る結果を示す。実施例のうち、接触部材に粉末を用いた試料番号２、試料番号５、試料番号８、試料番号１１では破損率が２０％以下と良好である。特に接触部材の材質がマグネシア（試料番号２）、スピネル（試料番号５）、ジルコニア（試料番号８）では破損率が０％と最も良好である。
【００２１】
破損率を低くするには、接触部材の材質はマグネシア、スピネル、ジルコニア、アルミナの順に好ましい。結晶構造（Ｘ線回折）の結果が示すように、マグネシア、スピネル、ジルコニア、アルミナの順にβ”アルミナ以外の結晶層が多く観察されることから、ベータアルミナ管の有底部と円筒側面部とを連結する接続部分のナトリウムイオン伝導率を下げる効果が利いていることがわかる。
【００２２】
【発明の効果】
本発明によれば、ナトリウム−硫黄電池を通常の数倍の電流密度で急速充放電運転を行った時に発生するベータアルミナセラミックス管の破損率を抑えたベータアルミナ管を提供可能である。ベータアルミナ管の有底部と円筒側面部とを連結する接続部分に電流集中を発生させないように、上記連結部のナトリウムイオン伝導率を円筒側面部や有底部に比べて小さくする、もしくはナトリウムイオン伝導率を実質的に無くすことで、ナトリウム−硫黄電池運転中に起こるベータアルミナセラミックス管破損を大幅に低減できる。
【図面の簡単な説明】
【図１】ベータアルミナ管の説明図。
【図２】本発明の一実施例を例示した説明図。
【図３】本発明の一実施例を例示した説明図。
【図４】本発明の一実施例を例示した説明図。
【図５】本発明の一実施例を例示した説明図。
【符号の説明】
１ ベータアルミナ管の成形体
２ 有底部
３ 円筒側面部
４ 接続部分
５ 非ナトリウムイオン伝導性部材の焼結体からなる治具
６ 非ナトリウムイオン伝導性部材の焼結体からなる柱状治具
７ 非ナトリウムイオン伝導性部材の焼結体からなる治具
８ 耐火材
９ 非ナトリウムイオン伝導性部材の粉末[0001]
[Industrial application fields]
The present invention relates to a bottomed cylindrical solid alumina tube used for a solid electrolyte tube of a sodium-sulfur battery.
[0002]
[Prior art]
Beta-alumina ceramics are being researched and developed as solid electrolytes for sodium-sulfur batteries by utilizing excellent sodium ion conductivity. In a sodium-sulfur battery, beta alumina ceramics also serve as a partition between the positive electrode chamber and the negative electrode chamber of the battery. When the partition wall breaks, both active materials react explosively, which is dangerous. Therefore, beta alumina ceramics are required to have high mechanical strength.
[0003]
In order to improve the mechanical strength, there has been proposed a method (US Pat. No. 4,358,516) in which high-purity zirconia fine particles that do not react with beta alumina are dispersed to reinforce ceramics. In addition, a method of pre-sintering by hot pressing to increase the sintering density (Japanese Patent Laid-Open No. 49-30407) and a method of removing coarse raw material powder of 100 to 200 μm at each stage of the beta alumina production process (special feature) (Kaihei 2-15576) has been proposed.
[0004]
[Problems to be solved by the invention]
Attempts to improve the strength of these ceramics have the effect of reducing beta alumina ceramic breakage during battery assembly, but are not effective against beta alumina ceramic tube breakage during battery operation.
[0005]
Battery damage that occurs during operation of the sodium-sulfur battery is likely to occur when operating at a high current density. Specifically, the breakage at the connecting portion connecting the bottomed portion of the beta alumina tube and the cylindrical side surface portion occurs at a considerable rate. As the mechanism of the occurrence of damage, the connecting part has a smaller radius of curvature than the cylindrical side part or the bottomed part, so that current concentration occurs at the connecting part, the temperature locally increases, and damage is caused by thermal stress. Conceivable.
[0006]
An object of the present invention is to provide a beta-alumina tube for a solid electrolyte of a sodium-sulfur battery having good sodium ion conduction characteristics, high strength, and high reliability that does not cause problems during battery operation and assembly. To do. In particular, the object is to reduce the breakage of the beta alumina tube that occurs during operation of the sodium-sulfur battery.
[0007]
[Means for Solving the Problems]
The present invention includes a connecting portion that connects a bottomed portion of a bottomed cylindrical beta-alumina tube and a cylindrical side surface portion, and at least a part of the connecting portion contacts a contact member made of magnesia, spinel, zirconia, or alumina. in which are formed by being fired at a state of being. The components of the present invention will be described below with reference to FIG. Here, the “bottomed portion” refers to 2 in FIG. 1, for example. Here, the “cylindrical side surface portion” refers to 3 in FIG. 1, for example. The “connection portion” here refers to 4 in FIG. 1, for example. With such a configuration, the generation of thermal stress can be reduced and the breakage of the beta alumina tube can be prevented by preventing the concentration of current to the connection portion and reducing the local heat generation.
[0008]
According to the first aspect of the present invention, at least a part of the connection part is baked in a state where a contact member made of magnesia, spinel, zirconia or alumina is in contact with the connection part . The gist is that spinel, zirconia or alumina is produced. The non-sodium ion conduction member cuts off the sodium ion conduction path of the beta alumina tube, so that local current concentration can be prevented, and the thermal stress applied to the connecting portion between the bottomed portion of the beta alumina tube and the cylindrical side surface is reduced. Thus, it is possible to prevent the beta alumina ceramic from being damaged.
[0009]
The magnesia, spinel, zirconia, and alumina of the present invention have substantially no sodium ion conductivity. Therefore, the mixed ceramics cut the sodium ion conduction path of the beta alumina tube to prevent local current concentration, reduce the thermal stress applied to the connecting portion between the bottomed portion of the beta alumina tube and the cylindrical side surface, Alumina ceramics can be prevented from being damaged.
[0010]
In the invention of
[0011]
In the invention of
[0012]
A specific example of the present invention is illustrated in FIG. As shown in FIG. 5, a
[0013]
As another specific example, there may be mentioned a method in which various jigs exemplified in the invention of claim 3 (see FIGS. 2 to 4) are replaced with molded bodies. However, the configuration of the present invention is not limited to the specific configuration illustrated in FIGS. 2 to 4 described above.
[0014]
As mentioned above, even if it uses any manufacturing method of
[0015]
【Example】
Preparation of beta alumina ceramics used alpha alumina and sodium carbonate as starting materials, and lithium carbonate as a stabilizer. α-alumina was a 99.9% pure raw material, and sodium carbonate and lithium carbonate were
[0016]
The pulverized beta alumina powder and yttria-stabilized zirconium oxide (3 parts by weight with respect to 100 parts by weight of the beta alumina pulverized powder) were mixed with an aqueous solvent to form a slurry, which was then spray-dried to obtain a granulated powder. The powder was formed into a tube shape having a length of 400 mm, an outer diameter of 45 mm, and a wall thickness of 2.5 mm after sintering, and was fired by holding at a predetermined temperature for 1 hour. Firing is a state in which a contact member made of magnesia, spinel, zirconia, and alumina as shown in Table 1 is brought into contact with a curved surface portion that is a connecting portion that connects a bottomed portion and a cylindrical side surface of a beta alumina bottomed cylindrical molded body ( Firing was performed in the state shown in FIG.
[0017]
With the test piece cut out from the beta alumina tube thus obtained, the bulk density was measured by a buoyancy method using ethanol, and the ratio (relative density) to the theoretical density was calculated. In addition, the sodium ion conductivity (specific resistance value) at 350 degrees was measured by a four-terminal method using a Na—Na cell while maintaining the beta alumina tube shape. Further, the internal pressure fracture strength of the beta alumina tube was measured. The internal pressure fracture strength is obtained by applying pressure to the entire inside of the beta alumina tube and calculating the strength at the time of fracture from the shape of the beta alumina tube. The internal pressure strength was measured with 8 beta alumina tubes for each lot, and the average value was obtained. Moreover, the composition of the said curved surface part cut out the beta alumina tube, and performed elemental analysis by EDS (energy dispersive X-ray spectroscopy). The crystal structure was identified by X-ray diffraction. The results are shown in Table 1.
[0018]
Furthermore, a sodium-sulfur battery was produced using a beta alumina tube of the same lot, and a charge / discharge test was conducted for the purpose of evaluating the reliability of the sodium-sulfur battery. The conditions are: 3 hours discharge at 330 ° C. (battery operating temperature), 1 hour pause, 3 hours charge, 1 hour pause charge / discharge cycle (rapid charge / discharge about 3 times normal load leveling) repeated 500 times, reliability Evaluated. If a battery failure occurs due to the breakage of beta alumina alumina, charging / discharging becomes impossible. Ten cells were prepared for each lot, and 500 continuous charge / discharge tests were performed. In each lot, the occurrence rate of defects due to beta-alumina cracks generated by charging and discharging up to 500 times was investigated. The results are shown in Table 1.
[0019]
[Table 1]
From the results shown in Table 1, the failure rate of Sample No. 1 to Sample No. 12 which is an example of the present invention is 30% or less, whereas the failure rate of Sample No. 13 which is a comparative example is inferior to 70%. Indicates. Among the examples, Sample No. 2, Sample No. 5, Sample No. 8, and Sample No. 11 using powder as the contact member have good breakage rates of 20% or less. In particular, when the material of the contact member is magnesia (sample number 2), spinel (sample number 5), or zirconia (sample number 8), the breakage rate is 0%, which is the best.
[0021]
In order to reduce the breakage rate, the contact member is preferably made of magnesia, spinel, zirconia, and alumina in this order. As the result of the crystal structure (X-ray diffraction) shows that many crystal layers other than β "alumina are observed in the order of magnesia, spinel, zirconia, and alumina. It can be seen that the effect of lowering the sodium ion conductivity of the connecting portion to be linked is effective.
[0022]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the beta alumina pipe | tube which suppressed the failure | damage rate of the beta alumina ceramic pipe | tube which generate | occur | produces when a sodium-sulfur battery is rapidly charged / discharged by the current density several times the normal can be provided. In order to prevent current concentration from occurring in the connecting part connecting the bottomed part of the beta alumina tube and the cylindrical side part, the sodium ion conductivity of the connecting part is made smaller than that of the cylindrical side part or bottomed part, or sodium ion conduction By substantially eliminating the rate, the beta alumina ceramic tube breakage that occurs during operation of the sodium-sulfur battery can be greatly reduced.
[Brief description of the drawings]
FIG. 1 is an explanatory diagram of a beta alumina tube.
FIG. 2 is an explanatory diagram illustrating an embodiment of the present invention.
FIG. 3 is an explanatory diagram illustrating an embodiment of the present invention.
FIG. 4 is an explanatory diagram illustrating an embodiment of the present invention.
FIG. 5 is an explanatory diagram illustrating an embodiment of the present invention.
[Explanation of symbols]
DESCRIPTION OF
Claims (3)
該ベータアルミナ管の有底部と円筒側面部とを連結する接続部分を備え、
前記接続部分の少なくとも一部に、マグネシア、スピネル、ジルコニアもしくはアルミナからなる接触部材を接触させた状態にて焼成することにより、前記接続部分の少なくとも一部に、マグネシア、スピネル、ジルコニアもしくはアルミナが生成することを特徴とするナトリウム−硫黄電池用ベータアルミナ管。A bottomed cylindrical beta alumina tube used for a solid electrolyte tube of a sodium-sulfur battery,
A connecting portion for connecting the bottomed portion and the cylindrical side surface of the beta alumina tube;
At least a portion of said connecting portion, magnesia, spinel, by firing in a state contacting the contact member made of zirconia or alumina, at least a portion of said connecting portion, magnesia, spinel, zirconia or alumina-yielding A beta alumina tube for a sodium-sulfur battery.
前記ベータアルミナ管の有底部と円筒側面部とを連結する接続部分の少なくとも一部に、マグネシア、スピネル、ジルコニアもしくはアルミナからなる接触部材を接触させた状態にて焼成することを特徴とするナトリウム−硫黄電池用ベータアルミナ管の製造方法。A method for producing a bottomed cylindrical beta alumina tube for use in a solid electrolyte tube of a sodium-sulfur battery, comprising:
Firing in a state where a contact member made of magnesia, spinel, zirconia or alumina is in contact with at least a part of the connecting portion connecting the bottomed portion and the cylindrical side surface portion of the beta alumina tube. A method for producing a beta alumina tube for a sulfur battery.
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| JP05212799A JP4365470B2 (en) | 1999-03-01 | 1999-03-01 | Beta-alumina tube for sodium-sulfur battery and method for producing the same |
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| JP05212799A JP4365470B2 (en) | 1999-03-01 | 1999-03-01 | Beta-alumina tube for sodium-sulfur battery and method for producing the same |
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