JP2014112474A - Solid electrolyte - Google Patents

Solid electrolyte Download PDF

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JP2014112474A
JP2014112474A JP2012266030A JP2012266030A JP2014112474A JP 2014112474 A JP2014112474 A JP 2014112474A JP 2012266030 A JP2012266030 A JP 2012266030A JP 2012266030 A JP2012266030 A JP 2012266030A JP 2014112474 A JP2014112474 A JP 2014112474A
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solid electrolyte
oxygen
sr12a7
sintered body
mayenite
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Satoru Fujita
悟 藤田
Masahiko Asaoka
賢彦 朝岡
Katsuro Hayashi
克郎 林
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Toyota Central R&D Labs Inc
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Toyota Central R&D Labs Inc
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Priority to DE102013005888.0A priority patent/DE102013005888B4/en
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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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    • Y02E60/50—Fuel cells

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Abstract

PROBLEM TO BE SOLVED: To provide a novel solid electrolyte having high oxygen-ion conduction properties.SOLUTION: A solid electrolyte comprises a sintered body of strontium aluminate (SrAlO:Sr12A7) having a structure in which oxygen ions (O) are included. The solid electrolyte may be used as an oxygen-ion (O) conductor. The solid electrolyte may be used also as an electrolyte of a solid oxide fuel cell (SOFC).

Description

本発明は、固体電解質に関し、さらに詳しくは、マイエナイト型化合物の一種であるストロンチウムアルミネート（Ｓｒ12Ａｌ14Ｏ33：Ｓｒ１２Ａ７）の焼結体からなる固体電解質に関する。 The present invention relates to a solid electrolyte, and more particularly to a solid electrolyte made of a sintered body of strontium aluminate (Sr 12 Al 14 O 33 : Sr12A7) which is a kind of mayenite type compound.

燃料電池は、環境問題・エネルギー問題を解決するための有力な手段の一つである。特に、固体酸化物型燃料電池（ＳＯＦＣ）は、（１）発電効率が高い、（２）多様な燃料に対応可能である、（３）小型分散電源から大規模火力代替システムまで幅広い適応性を持つ、（４）Ｐｔ触媒を必要としない、等の利点がある。
しかし、本格的な市場拡大のためには、（１）作動温度の低温下（１０００℃から６００℃以下）、（２）耐久性（熱的・機械的強度の確保、緊急停止繰り返し等）の向上、（３）セル構造の最適化、等が必要条件となっている。 A fuel cell is one of the effective means for solving environmental problems and energy problems. In particular, solid oxide fuel cells (SOFC) are (1) high power generation efficiency, (2) compatible with various fuels, and (3) wide applicability from small distributed power sources to large-scale thermal power alternative systems. (4) It does not require a Pt catalyst.
However, for full-scale market expansion, (1) under low operating temperature (1000 ° C to 600 ° C or less), (2) durability (ensure thermal and mechanical strength, repeated emergency stop, etc.) Improvements, (3) optimization of the cell structure, etc. are necessary conditions.

特に、作動温度を低温下させるためには、電解質、アノード・カソード、触媒等の材料設計は重要である。現在、電解質材料として、イットリア安定化ジルコニア（ＹＳＺ）、ランタンガレート等が知られている。しかしながら、６００℃での高伝導化（〜０．１Ｓ／ｃｍ）が達成された例は、従来にはない。   In particular, in order to lower the operating temperature, the material design of the electrolyte, anode / cathode, catalyst, etc. is important. Currently, yttria stabilized zirconia (YSZ), lanthanum gallate, and the like are known as electrolyte materials. However, there is no example in which high conductivity (˜0.1 S / cm) at 600 ° C. has been achieved.

一方、マイエナイト（Ｃａ12Ａｌ14Ｏ33：Ｃ１２Ａ７）は、Ａｌ−Ｏ四面体骨格から構成されるケージ（ナノ細孔）と、ケージ内に包摂されたＣａイオン及び酸素イオンとを備えた材料である。ナノ細孔は、酸素イオンや電子の伝導チャンネルとして機能すると考えられている。そのため、マイエナイト及びこれに類似の構造を備えた化合物（マイエナイト型化合物）の導電性に関し、従来から種々の検討が行われている。 On the other hand, mayenite (Ca 12 Al 14 O 33 : C12A7) is a material comprising a cage (nanopore) composed of an Al—O tetrahedral skeleton, and Ca ions and oxygen ions included in the cage. is there. Nanopores are thought to function as conduction channels for oxygen ions and electrons. For this reason, various studies have been conventionally conducted on the conductivity of mayenite and a compound (mayenite type compound) having a similar structure.

例えば、特許文献１には、
（１）炭酸カルシウム：酸化アルミニウム＝１２：７の混合物を大気雰囲気下、１３００℃で６時間保持し、
（２）得られた焼結物（Ｃ１２Ａ７）を粉砕して平均粒径が５０μｍの粉末Ａとし、
（３）粉末Ａに炭素粉末を加えて成形し、成形体を酸素濃度０．６体積％の窒素ガス雰囲気下において、１３００℃で２時間保持する
ことにより得られる導電性マイエナイト型化合物が開示されている。
同文献には、粉末Ａは絶縁体であるのに対し、導電性マイエナイト型化合物の電子密度は１．５×１０20／ｃｍ3である点（すなわち、電子伝導体として機能する点）が記載されている。 For example, Patent Document 1 discloses that
(1) A mixture of calcium carbonate: aluminum oxide = 12: 7 is held at 1300 ° C. for 6 hours in an air atmosphere,
(2) The obtained sintered product (C12A7) is pulverized into a powder A having an average particle size of 50 μm,
(3) Disclosed is a conductive mayenite type compound obtained by adding carbon powder to powder A and molding and holding the molded body at 1300 ° C. for 2 hours in a nitrogen gas atmosphere having an oxygen concentration of 0.6 vol%. ing.
This document describes that powder A is an insulator, whereas the electron density of the conductive mayenite type compound is 1.5 × 10 20 / cm 3 (that is, it functions as an electron conductor). Has been.

また、特許文献２には、Ｃｕ／Ｃａ比が０．０５又は０．０２５であるアルミノケイ酸カルシウム（Ｃａ12(Ａｌ14-xＳｉx)Ｏ33+0.5x、０＜ｘ≦４）のＣｕ置換体からなる粉末、及び、Ｃｒ／Ｃａ比が０．０５であるアルミノケイ酸カルシウムのＣｒ置換体からなる粉末が開示されている。
同文献には、
（１）アルミノケイ酸カルシウム（マイエナイト）は、構造中に酸化物イオン（Ｏ2 -）が包蔵されている点、及び、
（２）アルミノケイ酸カルシウムのＣａの一部をＣｕ又はＣｒで置換すると、酸素貯蔵能が増大する点、
が記載されている。 Patent Document 2 discloses Cu of calcium aluminosilicate (Ca 12 (Al 14 -x Si x ) O 33 + 0.5x , 0 <x ≦ 4) having a Cu / Ca ratio of 0.05 or 0.025. Disclosed are powders made of substitution products and powders made of Cr substitution products of calcium aluminosilicate having a Cr / Ca ratio of 0.05.
In the same document,
(1) Calcium aluminosilicate (mayenite) contains oxide ions (O 2 − ) in its structure, and
(2) When a part of Ca of calcium aluminosilicate is replaced with Cu or Cr, the oxygen storage capacity increases.
Is described.

さらに、特許文献３には、
（１）水酸化ストロンチウムとγ−アルミナの混合粉末を成形し、
（２）成形体を大気中で、８００℃で２時間焼成して固相反応させ、
（３）その後、室温まで約１００℃／秒の速度で急冷し、
（４）さらに、得られた化合物を、酸素１気圧の乾燥雰囲気中で、５５０℃で１２時間再焼成する
ことにより得られる１２ＳｒＯ・７Ａｌ2Ｏ3化合物が開示されている。
同文献には、得られた化合物には、４×１０19／ｃｍ3のＯ2 -ラジカルと、１×１０19／ｃｍ3のＯ-ラジカルが含まれている点が記載されている。 Furthermore, Patent Document 3 includes:
(1) Molding a mixed powder of strontium hydroxide and γ-alumina,
(2) The molded body is fired at 800 ° C. for 2 hours in the air to cause a solid phase reaction,
(3) After that, rapidly cool to room temperature at a rate of about 100 ° C./second
(4) Further, a 12SrO · 7Al 2 O 3 compound obtained by re-baking the obtained compound at 550 ° C. for 12 hours in a dry atmosphere of 1 atmosphere of oxygen is disclosed.
The same document, the resulting compound of 4 × 10 19 / cm 3 O 2 - radical, of 1 × 10 19 / cm 3 O - is that it contains a radical is described.

上述した文献に記載されているように、マイエナイトを還元処理したり、あるいは、マイエナイトのＣａサイト又はＡｌサイトの一部を他の元素で置換すると、マイエナイトの伝導特性が変化することが知られている。しかしながら、ＹＳＺと同等以上の酸素イオン伝導特性を持つマイエナイト型化合物からなる固体電解質が提案された例は、従来にはない。   As described in the above-mentioned documents, it is known that when mayenite is reduced or a part of Ca site or Al site of mayenite is replaced with another element, the conduction property of mayenite changes. Yes. However, there has never been an example in which a solid electrolyte made of a mayenite type compound having oxygen ion conduction characteristics equivalent to or better than YSZ has been proposed.

国際公開第２００６／１２９６７５号International Publication No. 2006/129675 特開２００７−０８３１２６号公報Japanese Patent Laid-Open No. 2007-083126 特許第４１０５４４７号公報Japanese Patent No. 4105447

本発明が解決しようとする課題は、高い酸素イオン伝導特性を持つ新規な固体電解質を提供することにある。   The problem to be solved by the present invention is to provide a novel solid electrolyte having high oxygen ion conductivity.

上記課題を解決するために本発明に係る固体電解質は、構造中に酸素イオン（Ｏ2-）が包摂されたストロンチウムアルミネート（Ｓｒ12Ａｌ14Ｏ33：Ｓｒ１２Ａ７）の焼結体からなる。 In order to solve the above problems, the solid electrolyte according to the present invention is composed of a sintered body of strontium aluminate (Sr 12 Al 14 O 33 : Sr12A7) in which oxygen ions (O 2− ) are included in the structure.

ＳｒイオンはＣａイオンに比べてイオン半径が大きい。そのため、Ｃ１２Ａ７のＣａサイトのすべてをＳｒで置換すると、格子定数が大きくなり、それに伴って構造内のイオンチャンネルも大きくなる。その結果、Ｓｒ１２Ａ７は、Ｃ１２Ａ７に比べて高いイオン伝導度を示す。このようなＳｒ１２Ａ７の焼結体を、例えばＳＯＦＣの電解質として用いると、Ｃ１２Ａ７を用いた場合に比べて、高い効率が得られる。   Sr ions have a larger ion radius than Ca ions. Therefore, when all of the Ca sites of C12A7 are replaced with Sr, the lattice constant increases, and the ion channel in the structure increases accordingly. As a result, Sr12A7 exhibits higher ionic conductivity than C12A7. When such a sintered body of Sr12A7 is used as, for example, an SOFC electrolyte, high efficiency can be obtained as compared with the case of using C12A7.

マイエナイト（Ｃ12Ａｌ14Ｏ33：Ｃ１２Ａ７）の結晶構造の模式図である。Mayenite (C 12 Al 14 O 33: C12A7) is a schematic view of the crystal structure of. Ｓｒ１２Ａ７とＣ１２Ａ７の格子定数の温度依存性を示す図である。It is a figure which shows the temperature dependence of the lattice constant of Sr12A7 and C12A7. 各種材料のイオン伝導度の温度依存性を示す図である。It is a figure which shows the temperature dependence of the ionic conductivity of various materials. Ｓｒ12Ａｌ14Ｏ33（左上図：相対密度５２％）及びＣａ12Ａｌ14Ｏ33（右上図：相対密度５０％、右下図：相対密度９５％）の断面写真である。It is a cross-sectional photograph of Sr 12 Al 14 O 33 (upper left figure: relative density 52%) and Ca 12 Al 14 O 33 (upper right figure: relative density 50%, lower right figure: relative density 95%).

以下、本発明の一実施の形態について詳細に説明する。
［１． 固体電解質］
本発明に係る固体電解質は、構造中に酸素イオン（Ｏ2-）が包摂されたストロンチウムアルミネート（Ｓｒ12Ａｌ14Ｏ33：Ｓｒ１２Ａ７）の焼結体からなる。 Hereinafter, an embodiment of the present invention will be described in detail.
[1. Solid electrolyte]
The solid electrolyte according to the present invention is made of a sintered body of strontium aluminate (Sr 12 Al 14 O 33 : Sr12A7) in which oxygen ions (O 2− ) are included in the structure.

［１．１． 結晶構造］
図１に、マイエナイト（Ｃ12Ａｌ14Ｏ33：Ｃ１２Ａ７）の結晶構造の模式図を示す。マイエナイトは、ゼオライト様構造をとり、Ａｌ−Ｏ四面体骨格と、その骨格から構成される０．６ｎｍのケージ（細孔）を有する。そのケージ内には、Ｃａイオンと酸素イオンが包摂されている。ＹＳＺのような酸素欠損サイトを介した酸素移動に比べて、マイエナイトは、既に酸素イオンが通るイオンチャンネルを備えているため、ケージ間（ナノ細孔を介したイオンチャンネル）における酸素イオンモビリティーの方が大きいものと予想される。 [1.1. Crystal structure]
1, mayenite: shows a schematic view of the crystal structure of (C 12 Al 14 O 33 C12A7 ). The mayenite has a zeolite-like structure and has an Al—O tetrahedral skeleton and a cage (pore) of 0.6 nm composed of the skeleton. The cage contains Ca ions and oxygen ions. Compared to oxygen transfer through oxygen deficient sites such as YSZ, mayenite already has ion channels through which oxygen ions pass, so oxygen ion mobility between cages (ion channels through nanopores) Is expected to be large.

本発明は、マイエナイトの酸素移動をさらに容易化するために、マイエナイトのＣａサイトのすべてをＳｒで置換したことを特徴とする。すなわち、本発明に係る固体電解質は、ストロンチウムアルミネート（Ｓｒ12Ａｌ14Ｏ33：Ｓｒ１２Ａ７）の焼結体からなる。Ｓｒ１２Ａ７は、Ｃ１２Ａ７と同様に、その構造中に酸素イオン（Ｏ2-）が包摂されている。Ｓｒ１２Ａ７からなる焼結体は、従来のＳＯＦＣ用固体電解質であるＹＳＺと同等以上の電気伝導度を示す可能性がある。 The present invention is characterized in that all of the Ca sites of the mayenite are substituted with Sr in order to further facilitate the oxygen transfer of the mayenite. That is, the solid electrolyte according to the present invention is made of a sintered body of strontium aluminate (Sr 12 Al 14 O 33 : Sr12A7). Similar to C12A7, Sr12A7 includes oxygen ions (O 2− ) in its structure. There is a possibility that a sintered body made of Sr12A7 has an electric conductivity equal to or higher than that of YSZ, which is a conventional solid electrolyte for SOFC.

［１．２． 相対密度］
一般に、固体電解質は、焼結密度が高くなるほど、伝導度が増大する。後述する方法を用いて本発明に係る固体電解質を製造すると、焼結体の相対密度は、５０％以上となる。 [1.2. Relative density]
In general, the conductivity of a solid electrolyte increases as the sintered density increases. When the solid electrolyte according to the present invention is manufactured using a method described later, the relative density of the sintered body is 50% or more.

［１．３． 用途］
本発明に係る固体電解質は、酸素イオン（Ｏ2-）伝導体として用いることができる。また、本発明に係る固体電解質は、固体酸化物型燃料電池（ＳＯＦＣ）の電解質として用いることができる。 [1.3. Application]
The solid electrolyte according to the present invention can be used as an oxygen ion (O 2− ) conductor. The solid electrolyte according to the present invention can be used as an electrolyte for a solid oxide fuel cell (SOFC).

［２． 固体電解質の製造方法］
本発明に係る固体電解質は、
（１）Ｓｒ源及びＡｌ源を所定の比率で混合し（混合工程）、
（２）混合物を成形し（成形工程）、
（３）成形体を焼結させる（焼結工程）
ことにより製造することができる。 [2. Method for producing solid electrolyte]
The solid electrolyte according to the present invention is:
(1) Sr source and Al source are mixed at a predetermined ratio (mixing step),
(2) Molding the mixture (molding process)
(3) Sintering the compact (sintering process)
Can be manufactured.

［２．１． 混合工程］
混合工程は、Ｓｒ源及びＡｌ源を所定の比率で混合する工程である。使用する原料は、Ｓｒ１２Ａ７を製造可能なものであれば良く、特に限定されない。
Ｓｒ源としては、例えば、炭酸ストロンチウム、酸化ストロンチウム、水酸化ストロンチウム、塩化ストロンチウム、酢酸ストロンチウム、硝酸ストロンチウムなどがある。
Ａｌ源としては、例えば、γアルミナ、αアルミナ、アルミナゾル、水酸化アルミニウム、硝酸アルミニウム、硫酸アルミニウム、塩化アルミニウム、窒化アルミニウム、ボーキサイトなどがある。 [2.1. Mixing process]
The mixing step is a step of mixing the Sr source and the Al source at a predetermined ratio. The raw material to be used is not particularly limited as long as it can produce Sr12A7.
Examples of the Sr source include strontium carbonate, strontium oxide, strontium hydroxide, strontium chloride, strontium acetate, and strontium nitrate.
Examples of the Al source include γ alumina, α alumina, alumina sol, aluminum hydroxide, aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum nitride, and bauxite.

原料の混合比率は、Ｓｒ１２Ａ７が得られる比率とする。混合方法は、特に限定されるものではなく、均一な原料混合物が得られる方法であれば良い。   The mixing ratio of the raw materials is a ratio at which Sr12A7 is obtained. The mixing method is not particularly limited as long as a uniform raw material mixture can be obtained.

［２．２． 成形工程］
成形工程は、混合物を成形する工程である。成形方法及び成形条件は、特に限定されるものではなく、高密度の成形体が得られる方法及び条件であればよい。 [2.2. Molding process]
The forming step is a step of forming the mixture. The molding method and molding conditions are not particularly limited as long as they are methods and conditions for obtaining a high-density molded body.

［２．３． 焼結工程］
焼結工程は、成形体を焼結させる工程である。焼結方法及び焼結条件は、特に限定されるものではなく、相対的に密度の高い焼結体が得られる方法及び条件であればよい。 [2.3. Sintering process]
A sintering process is a process of sintering a molded object. The sintering method and sintering conditions are not particularly limited, and may be any method and conditions that can obtain a sintered body having a relatively high density.

［３． 作用］
ＳｒイオンはＣａイオンに比べてイオン半径が大きい。そのため、Ｃ１２Ａ７のＣａサイトのすべてをＳｒで置換すると、格子定数が大きくなり、それに伴って構造内のイオンチャンネルも大きくなる。その結果、Ｓｒ１２Ａ７は、Ｃ１２Ａ７に比べて高いイオン伝導度を示す。このようなＳｒ１２Ａ７の焼結体を、例えばＳＯＦＣの電解質として用いると、Ｃ１２Ａ７を用いた場合に比べて、高い効率が得られる。 [3. Action]
Sr ions have a larger ion radius than Ca ions. Therefore, when all of the Ca sites of C12A7 are replaced with Sr, the lattice constant increases, and the ion channel in the structure increases accordingly. As a result, Sr12A7 exhibits higher ionic conductivity than C12A7. When such a sintered body of Sr12A7 is used as, for example, an SOFC electrolyte, high efficiency can be obtained as compared with the case of using C12A7.

（実施例１、比較例１〜３）
［１． 試料の作製（実施例１）］
Ｓｒ(ＯＨ)2・８Ｈ2Ｏ粉末（(株)高純度化学研究所製）と、γ−Ａｌ2Ｏ3（(株)高純度化学研究所製）をモル比で１２：７となる比率で、総量約２０ｇを秤量した。これを容積５００ｍＬのナイロンポット製の容器に入れ、さらに容器にジルコニアボール約６０ｇ、及び、エタノール約１５０ｍＬを加えて封止した。遊星ボールミル装置（三庄インダストリー(株)製）を用いて、２００ｒｐｍで２時間混合粉砕した。 (Example 1, Comparative Examples 1-3)
[1. Preparation of sample (Example 1)]
Sr (OH) 2 · 8H 2 O powder and (Co. Kojundo Chemical Laboratory, Ltd.), γ-Al 2 O 3 in (Co. Kojundo Chemical Laboratory, Ltd.) molar ratio of 12: 7 to become Ratio The total amount of about 20 g was weighed. This was put into a nylon pot container having a volume of 500 mL, and further, about 60 g of zirconia balls and about 150 mL of ethanol were added to the container and sealed. Using a planetary ball mill apparatus (manufactured by Sanjo Industry Co., Ltd.), the mixture was pulverized at 200 rpm for 2 hours.

乾燥した混合粉末約１．２ｇを直径２０ｍｍの金型を用いて４０ＭＰａの片押し成型の後、３００ＭＰａの冷間静水圧プレスを施して円盤状の圧粉体を得た。これを蒸留水が入った洗瓶を通すことで得られる加湿アルゴンガス又は窒素の気流中で、８００℃で６時間の条件で焼結を行い、炉冷してＳｒ１２Ａ７焼結体を得た。   About 1.2 g of the dried mixed powder was pressed at 40 MPa using a die having a diameter of 20 mm, and then subjected to a 300 MPa cold isostatic press to obtain a disk-shaped green compact. This was sintered in a humidified argon gas or nitrogen stream obtained by passing it through a washing bottle containing distilled water at 800 ° C. for 6 hours, and cooled in a furnace to obtain an Sr12A7 sintered body.

［２． 試料の作製（比較例１〜３）］
炭酸カルシウム（１８．７ｇ）及びγアルミナ（１１．１ｇ）を原料に用いた以外は、実施例１と同様にして、混合粉砕粉を作製した。次いで、混合粉砕粉の仮焼を行った。なお、仮焼条件は、１１００℃×１５時間とした。
次に、得られた仮焼粉を用いて焼結体（Ｃ１２Ａ７）を作製した。焼結条件は、１３５０℃×１２時間、大気雰囲気中（比較例１）、又は、１３５０℃×１２時間、酸素１００％雰囲気中（比較例２）とした。
さらに、市販のＹＳＺ（ＺｒＯ2−８ｍｏｌ％Ｙ2Ｏ3）をそのまま試験に供した（比較例３）。 [2. Preparation of sample (Comparative Examples 1 to 3)]
A mixed pulverized powder was produced in the same manner as in Example 1 except that calcium carbonate (18.7 g) and γ-alumina (11.1 g) were used as raw materials. Subsequently, the mixed pulverized powder was calcined. The calcining conditions were 1100 ° C. × 15 hours.
Next, a sintered body (C12A7) was produced using the obtained calcined powder. The sintering conditions were 1350 ° C. × 12 hours in an air atmosphere (Comparative Example 1) or 1350 ° C. × 12 hours in an oxygen 100% atmosphere (Comparative Example 2).
Furthermore, commercially available YSZ (ZrO 2 -8 mol% Y 2 O 3 ) was used for the test as it was (Comparative Example 3).

［３． 試験方法］
［３．１． 格子定数］
得られた焼結体について、Ｘ線回折を行った。測定温度は、室温から１０００℃とした。回折ピークから格子定数を算出した。
［３．２． 相対密度］
得られた焼結体の体積及び重量を測定し、密度を算出した。これを理論密度（Ｓｒ１２Ａ７の場合は、３．４４ｇ／ｃｍ3）で除して、相対密度とした。
［３．３． 伝導度測定］
焼結体の上下面に白金電極を付け、ＬＣＲメーターを用いて、２端子で膜厚方向のコンダクタンスを評価した。測定は、１００％のＯ2雰囲気下において、最高９００℃まで行った。 [3. Test method]
[3.1. Lattice constant]
The obtained sintered body was subjected to X-ray diffraction. The measurement temperature was from room temperature to 1000 ° C. The lattice constant was calculated from the diffraction peak.
[3.2. Relative density]
The volume and weight of the obtained sintered body were measured, and the density was calculated. This was divided by the theoretical density (3.44 g / cm 3 in the case of Sr12A7) to obtain a relative density.
[3.3. Conductivity measurement]
Platinum electrodes were attached to the upper and lower surfaces of the sintered body, and the conductance in the film thickness direction was evaluated with two terminals using an LCR meter. The measurement was performed up to 900 ° C. in a 100% O 2 atmosphere.

［４． 結果］
［４．１． 格子定数］
図２に、Ｓｒ１２Ａ７とＣ１２Ａ７の格子定数の温度依存性を示す。図２より、Ｓｒ１２Ａ７は、Ｃ１２Ａ７に比べて格子定数が大きいことがわかる。これは、Ｓｒイオンのイオン半径がＣａイオンより大きいためである。 [4. result]
[4.1. Lattice constant]
FIG. 2 shows the temperature dependence of the lattice constants of Sr12A7 and C12A7. FIG. 2 shows that Sr12A7 has a larger lattice constant than C12A7. This is because the ionic radius of Sr ions is larger than Ca ions.

［４．２． 相対密度］
実施例１の焼結体の相対密度は、５２％であった。一方、比較例１、２の焼結体の相対密度は、それぞれ、５０％及び９５％であった。 [4.2. Relative density]
The relative density of the sintered body of Example 1 was 52%. On the other hand, the relative densities of the sintered bodies of Comparative Examples 1 and 2 were 50% and 95%, respectively.

［４．３． 伝導度］
図３に、各種材料のイオン伝導度の温度依存性を示す。なお、図３中の（）内の数値は、相対密度（％）を表す。また、図４に、Ｓｒ12Ａｌ14Ｏ33（左上図：相対密度５２％）及びＣａ12Ａｌ14Ｏ33（右上図：相対密度５０％、右下図：相対密度９５％）の断面写真を示す。図３及び図４より、以下のことが分かる。
（１）相対密度が同等（約５０％）である場合、Ｓｒ12Ａｌ14Ｏ33の伝導度は、Ｃａ12Ａｌ14Ｏ33より高い。
（２）相対密度が５２％であるＳｒ12Ａｌ14Ｏ33の伝導度は、相対密度が９５％であるＣａ12Ａｌ14Ｏ33とほぼ同等の伝導度を示す。 [4.3. Conductivity]
FIG. 3 shows the temperature dependence of the ionic conductivity of various materials. In addition, the numerical value in () in FIG. 3 represents a relative density (%). FIG. 4 shows cross-sectional photographs of Sr 12 Al 14 O 33 (upper left: relative density 52%) and Ca 12 Al 14 O 33 (upper right: relative density 50%, lower right: 95% relative density). . 3 and 4 show the following.
(1) When the relative density is equivalent (about 50%), the conductivity of Sr 12 Al 14 O 33 is higher than that of Ca 12 Al 14 O 33 .
(2) The conductivity of Sr 12 Al 14 O 33 having a relative density of 52% is almost the same as that of Ca 12 Al 14 O 33 having a relative density of 95%.

以上、本発明の実施の形態について詳細に説明したが、本発明は上記実施の形態に何ら限定されるものではなく、本発明の要旨を逸脱しない範囲内で種々の改変が可能である。   Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above embodiments, and various modifications can be made without departing from the scope of the present invention.

本発明に係る固体電解質は、燃料電池用の電解質膜、酸素センサー、酸化触媒（排ガス浄化触媒、燃焼触媒、部分酸化触媒）などに使用することができる。   The solid electrolyte according to the present invention can be used for an electrolyte membrane for a fuel cell, an oxygen sensor, an oxidation catalyst (exhaust gas purification catalyst, combustion catalyst, partial oxidation catalyst) and the like.

Claims (3)

構造中に酸素イオン（Ｏ2-）が包摂されたストロンチウムアルミネート（Ｓｒ12Ａｌ14Ｏ33：Ｓｒ１２Ａ７）の焼結体からなる固体電解質。 A solid electrolyte comprising a sintered body of strontium aluminate (Sr 12 Al 14 O 33 : Sr12A7) in which oxygen ions (O 2− ) are included in the structure. 酸素イオン（Ｏ2-）伝導体として用いられる請求項１に記載の固体電解質。 The solid electrolyte according to claim 1, which is used as an oxygen ion (O 2− ) conductor. 固体酸化物型燃料電池（ＳＯＦＣ）の電解質として用いられる請求項１に記載の固体電解質。   The solid electrolyte according to claim 1, which is used as an electrolyte of a solid oxide fuel cell (SOFC).
JP2012266030A 2012-04-05 2012-12-05 Solid electrolyte Pending JP2014112474A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023105948A1 (en) * 2021-12-08 2023-06-15 Ａｇｃ株式会社 Sealing material, and sofc or soec having sealing material

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003128415A (en) * 2001-10-18 2003-05-08 Japan Science & Technology Corp 12CaO-7Al2O3 COMPOUND AND METHOD FOR PREPARING THE SAME
JP2003238149A (en) * 2002-02-21 2003-08-27 Japan Science & Technology Corp 12SrO/7AL2O3 COMPOUND AND ITS SYNTHESIZING METHOD
WO2004082050A1 (en) * 2003-03-14 2004-09-23 Thinktank Phoenix Ltd. Honeycomb type solid electrolytic fuel cell
JP2006080006A (en) * 2004-09-10 2006-03-23 Think Tank Phoenix:Kk Internal cooling regenerating type honeycomb-shaped solid oxide fuel cell
JP2006133039A (en) * 2004-11-04 2006-05-25 Riken Corp Nitrogen oxide sensor
JP2012025279A (en) * 2010-07-23 2012-02-09 Oxy Japan:Kk Air cleaner, and filter unit
US20120153806A1 (en) * 2009-08-25 2012-06-21 Asahi Glass Company, Limited Electrode for discharge lamp, method of manufacturing electrode for discharge lamp, and discharge lamp
JP2012119327A (en) * 2012-01-23 2012-06-21 Toho Gas Co Ltd High ion-conductivity solid electrolytic material, sintered compact, and solid electrolyte fuel battery

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003128415A (en) * 2001-10-18 2003-05-08 Japan Science & Technology Corp 12CaO-7Al2O3 COMPOUND AND METHOD FOR PREPARING THE SAME
JP2003238149A (en) * 2002-02-21 2003-08-27 Japan Science & Technology Corp 12SrO/7AL2O3 COMPOUND AND ITS SYNTHESIZING METHOD
WO2004082050A1 (en) * 2003-03-14 2004-09-23 Thinktank Phoenix Ltd. Honeycomb type solid electrolytic fuel cell
JP2006080006A (en) * 2004-09-10 2006-03-23 Think Tank Phoenix:Kk Internal cooling regenerating type honeycomb-shaped solid oxide fuel cell
JP2006133039A (en) * 2004-11-04 2006-05-25 Riken Corp Nitrogen oxide sensor
US20120153806A1 (en) * 2009-08-25 2012-06-21 Asahi Glass Company, Limited Electrode for discharge lamp, method of manufacturing electrode for discharge lamp, and discharge lamp
JP2012025279A (en) * 2010-07-23 2012-02-09 Oxy Japan:Kk Air cleaner, and filter unit
JP2012119327A (en) * 2012-01-23 2012-06-21 Toho Gas Co Ltd High ion-conductivity solid electrolytic material, sintered compact, and solid electrolyte fuel battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023105948A1 (en) * 2021-12-08 2023-06-15 Ａｇｃ株式会社 Sealing material, and sofc or soec having sealing material

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