JPH09183657A - Solid electrolyte - Google Patents
Solid electrolyteInfo
- Publication number
- JPH09183657A JPH09183657A JP7342746A JP34274695A JPH09183657A JP H09183657 A JPH09183657 A JP H09183657A JP 7342746 A JP7342746 A JP 7342746A JP 34274695 A JP34274695 A JP 34274695A JP H09183657 A JPH09183657 A JP H09183657A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- oxygen
- sintered body
- conductivity
- metal elements
- 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.)
- Pending
Links
Classifications
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Fuel Cell (AREA)
Abstract
(57)【要約】
【課題】 酸素欠陥の秩序−無秩序転移点の温度が
低く、転移に際して２．５桁以上の導電率の向上を示す
新規な酸素イオン伝導性固体電解質を提供する。
【解決手段】 組成が一般式：Ｂａ3 Ｍ4 Ｏ9 （式中、
Ｍは、酸素６配位を仮定した場合のイオン半径が０．９
０〜０．９７オングストロ−ムである３価の金属元素か
ら選ばれる一種又は二種以上の金属元素）で表され、そ
の結晶相が六方晶単一相である焼結体よりなる固体電解
質。(57) Abstract: A novel oxygen-ion conductive solid electrolyte having a low temperature of the order-disorder transition point of oxygen defects and exhibiting an increase in conductivity of 2.5 digits or more at the time of transition is provided. The composition has a general formula: Ba 3 M 4 O 9 (in the formula,
M has an ionic radius of 0.9 assuming oxygen 6 coordination.
A solid electrolyte composed of a sintered body represented by one or two or more metal elements selected from trivalent metal elements of 0 to 0.97 angstrom, and the crystal phase of which is a hexagonal single phase.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、燃料電池用セル材
料、あるいは、温度又は酸素センサ等に用いられる酸素
イオン伝導性固体電解質に関するものである。TECHNICAL FIELD The present invention relates to a cell material for a fuel cell, or an oxygen ion conductive solid electrolyte used for a temperature or oxygen sensor or the like.
【０００２】[0002]
【従来の技術】Ａ2 Ｂ2 Ｏ5 の組成を有する化合物は、
ブラウンミラ−ライト（Ｃａ2 Ｆｅ2 O5 ）型の結晶構造
を有し、ブラウンミラ−ライト型化合物と呼ばれてい
る。この化合物はＢサイトが３価の原子で構成されてお
り、ＡＢＯ3 （Ａサイトは２価、Ｂサイトは４価原子が
占める）で表されるペロブスカイト型化合物に比してＢ
サイトの原子価が低いことが特徴である。そのため、Ｂ
ａ2 Ｉｎ2 Ｏ5 やＳｒ2Ｆｅ2 Ｏ5 等では、ある特定の
温度において、酸素欠陥の秩序−無秩序転移を生じ、そ
の温度以上では酸素欠陥が無秩序化して、欠陥ペロブス
カイト構造になることが知られている（Ｓ．Ｓｈｉｎ
ａｎｄ Ｍ．Ｙｏｎｅｍｕｒａ，Ｍａｔ．Ｒｅｓ．Ｂｕ
ｌｌ．，ｖｏｌ．１３，ｐ．１０１７〜１０２１（１９
７８））。2. Description of the Related Art A compound having a composition of A 2 B 2 O 5 is
It has a brown mirror light (Ca 2 Fe 2 O 5 ) type crystal structure and is called a brown mirror light type compound. In this compound, the B site is composed of trivalent atoms, and compared with the perovskite type compound represented by ABO 3 (A site is divalent, B site is tetravalent atom)
The site is characterized by low valence. Therefore, B
In a 2 In 2 O 5 or Sr 2 Fe 2 O 5 or the like, in certain temperature, order of oxygen defects - cause disorder transition at that temperature above by disordered oxygen defect, can become defective perovskite structure Known (S. Shin
and M.D. Yonemura, Mat. Res. Bu
ll. , Vol. 13, p. 1017 to 1021 (19
78)).
【０００３】一方、Ａ3 Ｂ4 Ｏ9 型化合物（Ａサイトは
２価，Ｂサイトは３価原子）は、Ａ2 Ｂ2 Ｏ5 ＋ＡＢ2
Ｏ4 と分割表示できることからも分かるように、ブラウ
ンミラ−ライト型結晶構造（Ａ2 Ｂ2 Ｏ5 ）とＣａＦｅ
2 Ｏ4 型結晶構造を合わせ持つ化合物であることから、
ブラウンミラ−ライト関連化合物と呼ばれている。この
ブラウンミラ−ライト関連化合物は、常温では六方晶構
造を示し、Ｂａ3 Ｙ4 O9 等の化合物が知られている。On the other hand, an A 3 B 4 O 9 type compound (A site is divalent, B site is trivalent atom) is A 2 B 2 O 5 + AB 2
As can be seen from the fact that it can be divided and displayed as O 4 , the brown mirror-light type crystal structure (A 2 B 2 O 5 ) and CaFe
Since it is a compound that also has a 2 O 4 type crystal structure,
It is called a brown mirror-light related compound. This Brown Miller-light related compound shows a hexagonal crystal structure at room temperature, and compounds such as Ba 3 Y 4 O 9 are known.
【０００４】ペロブスカイト型化合物では、酸素欠陥が
イオン伝導の担い手と考えられており、酸素欠陥の移動
度が大きく向上するとイオン伝導度も大きく向上する。
Ｂａ2 Ｉｎ2 Ｏ5 は９３０℃程度に酸素欠陥の秩序−無
秩序転移点を有し、この温度よりも高い温度では酸素欠
陥が無秩序配列をして立方晶構造となり、イオン伝導率
が該転移点より低い温度におけるそれに比べて数十倍に
向上することが知られている。（Ｊ．Ｂ．Ｇｏｏｄｅｎ
ｏｕｇｈ，Ｊ．Ｅ．Ｒｕｉｚ−Ｄｉａｇ ａｎｄ Ｙ．
Ｓ．Ｚｈｅｎ， Ｓｏｌｉｄ Ｓｔａｔｅ Ｉｏｎｉｃ
ｓ，４４，ｐ．２１−３１（１９９０）） しかしながら、このＢａ2 Ｉｎ2 Ｏ5 にしても、酸素欠
陥の秩序−無秩序転移点の温度が９３０℃と高く、燃料
電池用セル材料、温度又は酸素センサとして使用するた
めには、この酸素欠陥の秩序−無秩序転移の転移点がさ
らに低い材料の開発が望まれている。In the perovskite type compound, oxygen defects are considered to be responsible for ionic conduction, and when the mobility of oxygen defects is greatly improved, the ionic conductivity is also greatly improved.
Ba 2 In 2 O 5 has an order-disorder transition point of oxygen defects at about 930 ° C., and at a temperature higher than this temperature, the oxygen defects have a disordered arrangement to form a cubic structure, and the ionic conductivity is the transition point. It is known to be several tens of times better than that at lower temperatures. (J. B. Gooden
Ough, J .; E. FIG. Ruiz-Diag and Y.
S. Zhen, Solid State Ionic
s, 44, p. 21-31 (1990)) However, even if this Ba 2 In 2 O 5 is used, the temperature of the order-disorder transition point of oxygen defects is as high as 930 ° C., and it is used as a cell material for fuel cells, a temperature, or an oxygen sensor. Therefore, it is desired to develop a material having a lower transition point of the order-disorder transition of oxygen defects.
【０００５】一方、従来報告されているＳｒ2 Ｆｅ2 Ｏ
5 の酸素欠陥の秩序−無秩序転移点は、昇温時には、７
８０℃、降温時には７００℃であり、この転移点が７０
０℃以上と高いばかりでなく、転移後のイオン伝導度も
転移前の状態に比して大きくは向上されないことが知ら
れている。On the other hand, the previously reported Sr 2 Fe 2 O
The order-disorder transition point of oxygen defect 5 is 7
80 ° C, 700 ° C when the temperature is lowered, and this transition point is 70
It is known that not only the temperature is higher than 0 ° C. but also the ionic conductivity after the transition is not significantly improved as compared with the state before the transition.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、酸素欠陥の
秩序−無秩序転移点の温度が低く、かつ転移時の導電率
の向上が飛躍的に大きい新規な酸素イオン伝導性固体電
解質の提供を目的とするものである。DISCLOSURE OF THE INVENTION The present invention provides a novel oxygen ion conductive solid electrolyte having a low temperature of the order-disorder transition point of oxygen defects and a dramatic increase in conductivity at the time of transition. It is intended.
【０００７】[0007]
【課題を解決するための手段】本発明の固体電解質は、
その組成が、一般式：Ｂａ3 Ｍ4 Ｏ9 （式中、Ｍは、酸
素６配位を仮定した場合のイオン半径が０．９０〜０．
９７オングストロ−ムである３価の金属元素）であるブ
ラウンミラ−ライト関連化合物からなることを特徴とす
る固体電解質である。また、本発明の固体電解質は、そ
の組成が、一般式：Ｂａ3 Ｍ4 Ｏ9 （式中、Ｍは、酸素
６配位を仮定した場合のイオン半径が０．９０〜０．９
７オングストロ−ムである３価の金属元素）で表され、
その結晶相が六方晶単一相である焼結体よりなることを
特徴とする固体電解質である。なお、酸素６配位を仮定
した場合のイオン半径が０．９０〜０．９７オングスト
ロームである３価の金属元素Ｍは、単一の金属元素であ
っても良いし、二種以上の金属元素であっても良い。こ
の３価の金属元素Ｍとしては、ジスプロシウム、ガドリ
ニウム及びサマリウムからなる群から選ばれる一種又は
二種以上の金属元素であることが更に好ましい。The solid electrolyte of the present invention comprises:
Its composition is represented by the general formula: Ba 3 M 4 O 9 (wherein M is an ionic radius of 0.90 to 0.
It is a solid electrolyte characterized in that it is composed of a brown-milarite-related compound which is a 97-angstrom trivalent metal element). Further, the composition of the solid electrolyte of the present invention has a general formula: Ba 3 M 4 O 9 (wherein, M is an ionic radius of 0.90 to 0.9 when oxygen 6-coordinate is assumed).
7 angstrom is a trivalent metal element),
It is a solid electrolyte characterized in that the crystal phase is a sintered body having a hexagonal single phase. The trivalent metal element M having an ionic radius of 0.90 to 0.97 angstrom assuming oxygen 6-coordination may be a single metal element, or two or more metal elements. May be The trivalent metal element M is more preferably one or more metal elements selected from the group consisting of dysprosium, gadolinium and samarium.
【０００８】以下に本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【０００９】一般式：Ｂａ3 Ｍ4 Ｏ9 中のＭは、酸素６
配位を仮定した場合のイオン半径が、０．９０〜０．９
７オングストロ−ムである３価の金属元素である。イオ
ン半径がこの範囲を下回ると、酸素欠陥の秩序−無秩序
転移による導電率の向上が小さくなり、特に、イオン半
径が０．８６オングストロームを下回ると、酸素欠陥の
秩序−無秩序転移が現れなくなり、導電率の向上は認め
られなくなるので好ましくない。また、この範囲を上回
るイオン半径を有する３価の金属元素を用いると、Ｍの
イオン半径が大きすぎることから、Ｂａ3 Ｍ4 Ｏ9 単一
相を作成することはできなくなり、固溶しきれないＭ元
素の酸化物が結晶粒界に析出し、導電率の著しい低下を
引き起こすため好ましくない。こうした条件を満たすＭ
元素の具体的な例としては、Ｄｙ（０．９１），Ｔｂ
（０．９２），Ｇｄ（０．９４），Ｅｕ（０．９５），
Ｂｋ（０．９６），Ｓｍ（０．９６）などがあげられる
が、取扱いの容易さなどから、Ｄｙ（０．９１），Ｇｄ
（０．９４），Ｓｍ（０．９６）などを選択することが
好ましい（ここでカッコ内の数字は酸素６配位を仮定し
た場合のイオン半径（オングストローム単位）を表
す）。このＭサイトに収納される３価の金属元素は、単
一の金属元素であっても良いし、二種以上の金属元素よ
りなり、それらがランダムに配置されて酸化物固溶体を
形成しているものであっても良い。In the general formula: Ba 3 M 4 O 9 , M is oxygen 6.
The ionic radius assuming coordination is 0.90 to 0.9
It is a trivalent metal element having a thickness of 7 angstroms. When the ionic radius is less than this range, the improvement in conductivity due to the order-disorder transition of oxygen defects becomes small. In particular, when the ionic radius is less than 0.86 angstrom, the order-disorder transition of oxygen defects does not appear and the conductivity is reduced. It is not preferable because the improvement of the rate cannot be recognized. Further, when a trivalent metal element having an ionic radius exceeding this range is used, the ionic radius of M is too large, so that it becomes impossible to form a Ba 3 M 4 O 9 single phase, and the solid solution is not completely dissolved. It is not preferable because the oxide of the element M which does not exist precipitates at the grain boundaries and causes a remarkable decrease in conductivity. M satisfying these conditions
Specific examples of the elements include Dy (0.91), Tb
(0.92), Gd (0.94), Eu (0.95),
Bk (0.96), Sm (0.96), etc. are listed, but Dy (0.91), Gd
(0.94), Sm (0.96), etc. are preferably selected (the numbers in parentheses represent the ionic radius (unit of Angstrom) assuming oxygen 6-coordination). The trivalent metal element accommodated in this M site may be a single metal element or may be composed of two or more kinds of metal elements, which are randomly arranged to form an oxide solid solution. It may be one.
【００１０】Ｍとして上記のイオン半径を有する３価の
金属元素を用い、上記の組成を有するブラウンミラ−ラ
イト関連化合物からなる固体電解質とすることにより、
すなわち、Ｍとして上記のイオン半径を有する３価の金
属元素を用い、上記の組成を有し、その結晶相が六方晶
単一相である焼結体からなる固体電解質とすることによ
り、３５０℃付近の低い温度において導電率の飛躍的な
向上を示す高イオン伝導体の作製が可能となる。By using a trivalent metal element having the above-mentioned ionic radius as M and forming a solid electrolyte composed of the Brown Miller-light related compound having the above-mentioned composition,
That is, by using a trivalent metal element having the above ionic radius as M and having the above composition and having a crystal phase of a hexagonal single phase as a solid electrolyte composed of a sintered body, 350 ° C. It becomes possible to fabricate a high ionic conductor that exhibits a dramatic improvement in conductivity at low temperatures in the vicinity.
【００１１】本発明の固体電解質の合成方法には特に制
限はなく、原料粉末として酸化物を用いて乾式及び湿式
混合により混合したのち焼成する方法、原料として無機
塩の水溶液を使用し沈澱剤としてシュウ酸などを用いる
ことによりシュウ酸塩として沈澱物を作製し、この沈澱
を濾過、乾燥したのち焼成する方法や、原料としてアル
コキシド溶液を使用し、液相混合したのち、加水分解反
応により沈澱を作製し、この沈澱を濾過、乾燥したのち
焼成する方法などを用いて合成することができる。The method for synthesizing the solid electrolyte of the present invention is not particularly limited, and a method in which an oxide as a raw material powder is used for mixing by dry and wet mixing and then firing, and an aqueous solution of an inorganic salt as a raw material is used as a precipitant. A precipitate is prepared as an oxalate salt by using oxalic acid, etc., and the precipitate is filtered, dried, and then calcined, or an alkoxide solution is used as a raw material, and liquid phase mixing is performed, followed by hydrolysis to precipitate the precipitate. It can be synthesized by a method in which the precipitate is prepared, and the precipitate is filtered, dried and then calcined.
【００１２】[0012]
【作用】本発明の効果発現の機構については、未だ十分
には解明されていないが、Ｂａ3 Ｍ4 Ｏ9 のＭサイトに
酸素６配位を仮定した場合のイオン半径が０．９０〜
０．９７オングストロ−ムである３価の金属元素を用い
ることにより、結晶に大きな歪みが導入され、結果とし
て結晶構造中の酸素イオンの通過可能な空間がひろが
り、Ｂａ2 Ｉｎ2 Ｏ5 などに見られる酸素欠陥の秩序−
無秩序転移点が８００℃付近から３５０℃付近へと低温
化するのみならず、この際に２．５桁以上導電率が向上
する結果が現れたものと考えられる。The mechanism of manifestation of the effects of the present invention has not been fully clarified yet, but the ionic radius is 0.90 to 0.90 assuming oxygen 6-coordination at the M site of Ba 3 M 4 O 9.
By using a trivalent metal element of 0.97 angstrom, a large strain is introduced into the crystal, and as a result, a space through which oxygen ions can pass in the crystal structure is expanded, and Ba 2 In 2 O 5 or the like is formed. Observed oxygen defect order-
It is considered that not only the disordered transition point is lowered from around 800 ° C. to around 350 ° C., but also the conductivity is improved by 2.5 digits or more.
【００１３】[0013]
【発明の効果】以上説明したように、本発明により、酸
素欠陥の秩序−無秩序転移点の温度が低く、かつ転移時
の導電率の向上が飛躍的に大きい新規な酸素イオン伝導
性固体電解質を得ることが可能となる。As described above, according to the present invention, a novel oxygen ion conductive solid electrolyte having a low temperature of the order-disorder transition point of oxygen defects and a dramatic increase in conductivity at the time of transition is provided. It becomes possible to obtain.
【００１４】[0014]
【実施例】以下、実施例により本発明を更に詳細に説明
するが、本発明はこれらに限定されるものではない。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.
【００１５】（実施例１）市販の炭酸バリウム（ＢａＣ
Ｏ3 ）粉末（キシダ化学製）５９．２ｇと、市販の酸化
ジスプロシウム（Ｄｙ2 Ｏ3 ）粉末（関東化学製）７
４．６ｇとを、エタノール中でボールミルを用いて十分
に混合したのち、１０００℃で、１時間大気中で仮焼し
た。得られた粉末を５００ｋｇ／ｃｍ2 の静水圧により
成形した後、１４００℃で５時間焼成して焼結体を作製
した。生成物の結晶相は、焼結体を粉末状に粉砕したの
ち、Ｘ線回折試験（ＣｕＫα線）を行うことにより同定
した。Example 1 Commercially available barium carbonate (BaC)
59.2 g of O 3 ) powder (manufactured by Kishida Chemical) and commercially available dysprosium oxide (Dy 2 O 3 ) powder (manufactured by Kanto Chemical) 7
4.6 g was thoroughly mixed with ethanol using a ball mill and then calcined in the atmosphere at 1000 ° C. for 1 hour. The obtained powder was molded under a hydrostatic pressure of 500 kg / cm 2 and then fired at 1400 ° C. for 5 hours to produce a sintered body. The crystal phase of the product was identified by performing an X-ray diffraction test (CuKα ray) after crushing the sintered body into a powder.
【００１６】Ｍ元素のイオン半径と得られた焼結体の組
成とその結晶構造の関係を表１に示す。Table 1 shows the relationship between the ionic radius of the M element, the composition of the obtained sintered body and its crystal structure.
【００１７】得られた焼結体に、８００℃において電極
の焼き付け処理を施すことにより白金電極を形成し、交
流２端子法によりその複素インピ−ダンスを測定して、
下記の式によりそのイオン伝導度を算出した。The obtained sintered body was subjected to an electrode baking treatment at 800 ° C. to form a platinum electrode, and its complex impedance was measured by an AC two-terminal method,
The ionic conductivity was calculated by the following formula.
【００１８】イオン伝導度：ｌｏｇσ＝ｌｏｇ｛Ｚｃｏ
ｓθ／（ｄ・Ｓ-1）｝ ここで、σは伝導度（イオン伝導度はこの値を対数とし
て示す）、Ｚはインピ−ダンス、θはおくれ角、ｄはペ
レットの厚み、Ｓはペレット上の白金電極面積をそれぞ
れ表す。Ionic conductivity: logσ = log {Zco
sθ / (d · S −1 )} where σ is the conductivity (ionic conductivity is expressed as a logarithm of this value), Z is the impedance, θ is the delay angle, d is the pellet thickness, and S is the pellet. The upper platinum electrode area is shown.
【００１９】得られた焼結体の２００℃から５００℃ま
でのイオン伝導度の値を表２に示す。Table 2 shows the values of the ionic conductivity of the obtained sintered body from 200 ° C to 500 ° C.
【００２０】（実施例２）市販の炭酸バリウム（ＢａＣ
Ｏ3 ）粉末（キシダ化学製）５９．２ｇと、市販の酸化
ガドリニウム（Ｇｄ2 Ｏ3 ）粉末（関東化学製）１４
５．０ｇとを用いたこと以外は全て実施例１と同様にし
て焼結体を作製し、実施例１と同様に生成物の結晶相を
Ｘ線回折試験（ＣｕＫα線）を行うことにより同定し
た。Ｍ元素のイオン半径と得られた焼結体の組成とその
結晶構造の関係を表１に示す。Example 2 Commercially available barium carbonate (BaC)
O 3 ) powder (manufactured by Kishida Chemical Co., Ltd.) 59.2 g and commercially available gadolinium oxide (Gd 2 O 3 ) powder (manufactured by Kanto Chemical Co., Ltd.) 14
A sintered body was produced in the same manner as in Example 1 except that 5.0 g was used, and the crystal phase of the product was identified by an X-ray diffraction test (CuKα ray) in the same manner as in Example 1. did. Table 1 shows the relationship between the ionic radius of the M element and the composition of the obtained sintered body and its crystal structure.
【００２１】また、実施例１と同様にして、得られた焼
結体のイオン伝導度を算出した。得られた焼結体の２０
０℃から５００℃までのイオン伝導度の値を表２に示
す。Further, the ionic conductivity of the obtained sintered body was calculated in the same manner as in Example 1. 20 of the obtained sintered body
Table 2 shows the values of ionic conductivity from 0 ° C to 500 ° C.
【００２２】（実施例３）市販の炭酸バリウム（ＢａＣ
Ｏ3 ）粉末（キシダ化学製）５９．２ｇと、市販の酸化
サマリウム（Ｓｍ2 Ｏ3 ）粉末（関東化学製）６９．８
ｇとを用いたこと以外は全て実施例１と同様にして焼結
体を作製し、実施例１と同様に生成物の結晶相をＸ線回
折試験（ＣｕＫα線）を行うことにより同定した。Ｍ元
素のイオン半径と得られた焼結体の組成とその結晶構造
の関係を表１に示す。Example 3 Commercially available barium carbonate (BaC)
O 3 ) powder (manufactured by Kishida Chemical Co., Ltd.) 59.2 g and commercially available samarium oxide (Sm 2 O 3 ) powder (manufactured by Kanto Kagaku Co., Ltd.) 69.8
A sintered body was produced in the same manner as in Example 1 except that g was used, and the crystal phase of the product was identified by performing an X-ray diffraction test (CuKα ray) in the same manner as in Example 1. Table 1 shows the relationship between the ionic radius of the M element and the composition of the obtained sintered body and its crystal structure.
【００２３】また、実施例１と同様にして、得られた焼
結体のイオン伝導度を算出した。得られた焼結体の２０
０℃から５００℃までのイオン伝導度の値を表２に示
す。In the same manner as in Example 1, the ionic conductivity of the obtained sintered body was calculated. 20 of the obtained sintered body
Table 2 shows the values of ionic conductivity from 0 ° C to 500 ° C.
【００２４】（実施例４）市販の炭酸バリウム（ＢａＣ
Ｏ3 ）粉末（キシダ化学製）５９．２ｇと、市販の酸化
ガドリニウム（Ｇｄ2 Ｏ3 ）粉末（関東化学製）３６．
３ｇ及び市販の酸化サマリウム（Ｓｍ2 Ｏ3 ）粉末（関
東化学製）３４．９ｇの３種の原料粉末を混合して用い
たこと以外は全て実施例１と同様にして焼結体を作製
し、実施例１と同様に生成物の結晶相をＸ線回折試験
（ＣｕＫα線）を行うことにより同定した。得られた焼
結体の組成とその結晶構造を表１に示す。Example 4 Commercially available barium carbonate (BaC)
O. 3 ) powder (manufactured by Kishida Chemical Co., Ltd.) 59.2 g and commercially available gadolinium oxide (Gd 2 O 3 ) powder (manufactured by Kanto Chemical Co., Ltd.) 36.
A sintered body was produced in the same manner as in Example 1 except that 3 g and 34.9 g of commercially available samarium oxide (Sm 2 O 3 ) powder (manufactured by Kanto Kagaku Co., Ltd.) were mixed and used. The crystal phase of the product was identified by performing an X-ray diffraction test (CuKα ray) in the same manner as in Example 1. Table 1 shows the composition and crystal structure of the obtained sintered body.
【００２５】また、実施例１と同様にして、得られた焼
結体のイオン伝導度を算出した。得られた焼結体の２０
０℃から５００℃までのイオン伝導度の値を表２に示
す。In the same manner as in Example 1, the ionic conductivity of the obtained sintered body was calculated. 20 of the obtained sintered body
Table 2 shows the values of ionic conductivity from 0 ° C to 500 ° C.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【表２】 [Table 2]
【００２８】（比較例１〜３）市販の炭酸バリウム（Ｂ
ａＣＯ3 ）粉末（キシダ化学製）５９．２ｇと市販の酸
化イッテルビウム（Ｙｂ2 Ｏ3 ）粉末（関東化学製）７
８．８ｇ（比較例１）、市販の炭酸バリウム（ＢａＣＯ
3 ）粉末（キシダ化学製）５９．２ｇと市販の酸化イッ
トリウム（Ｙ2 Ｏ3 ）粉末（関東化学製）４５．２ｇ
（比較例２）、市販の炭酸バリウム（ＢａＣＯ3 ）粉末
（キシダ化学製）５９．２ｇと市販の酸化エルビウム
（Ｅｒ2 Ｏ3 ）粉末（関東化学製）７６．５ｇ（比較例
３）とをそれぞれ用いたこと以外は全て実施例１と同様
にして焼結体を作製し、実施例１と同様に生成物の結晶
相をＸ線回折試験（ＣｕＫα線）を行うことにより同定
した。Ｍ元素のイオン半径と得られた焼結体の組成とそ
の結晶構造の関係を表３に示す。Comparative Examples 1 to 3 Commercially available barium carbonate (B
59.2 g of aCO 3 ) powder (manufactured by Kishida Chemical) and commercially available ytterbium oxide (Yb 2 O 3 ) powder (manufactured by Kanto Chemical) 7
8.8 g (Comparative Example 1), commercially available barium carbonate (BaCO
3 ) Powder (manufactured by Kishida Chemical) 59.2 g and commercially available yttrium oxide (Y 2 O 3 ) powder (manufactured by Kanto Chemical) 45.2 g
(Comparative Example 2), 59.2 g of commercially available barium carbonate (BaCO 3 ) powder (manufactured by Kishida Chemical) and 76.5 g of commercially available erbium oxide (Er 2 O 3 ) powder (manufactured by Kanto Kagaku) (Comparative Example 3) were used. A sintered body was produced in the same manner as in Example 1 except that each was used, and the crystal phase of the product was identified by performing an X-ray diffraction test (CuKα ray) in the same manner as in Example 1. Table 3 shows the relationship between the ionic radius of the M element and the composition of the obtained sintered body and its crystal structure.
【００２９】また、実施例１と同様にして、得られた焼
結体のイオン伝導度を算出した。得られた焼結体の２０
０℃から５００℃までのイオン伝導度の値を表４に示
す。In the same manner as in Example 1, the ionic conductivity of the obtained sintered body was calculated. 20 of the obtained sintered body
Table 4 shows the values of ionic conductivity from 0 ° C to 500 ° C.
【００３０】（比較例４、比較例５）市販の炭酸バリウ
ム（ＢａＣＯ3 ）粉末（キシダ化学製）５９．２ｇと市
販の酸化ネオジウム（Ｎｄ2 Ｏ3 ）粉末（関東化学製）
６７．３ｇ（比較例４）、市販の炭酸バリウム（ＢａＣ
Ｏ3 ）粉末（キシダ化学製）５９．２ｇと市販の酸化ラ
ンタン（Ｌａ2 Ｏ3 ）粉末（関東化学製）６５．２ｇ
（比較例５）とをそれぞれ用いたこと以外は全て実施例
１と同様にして焼結体を作製し、実施例１と同様に生成
物の結晶相をＸ線回折試験（ＣｕＫα線）を行うことに
より同定することを試みた。Comparative Examples 4 and 5 59.2 g of commercially available barium carbonate (BaCO 3 ) powder (manufactured by Kishida Chemical Co., Ltd.) and commercially available neodymium oxide (Nd 2 O 3 ) powder (manufactured by Kanto Chemical Co., Ltd.)
67.3 g (Comparative Example 4), commercially available barium carbonate (BaC
O 3 ) powder (manufactured by Kishida Chemical Co., Ltd.) 59.2 g and commercially available lanthanum oxide (La 2 O 3 ) powder (manufactured by Kanto Chemical Co., Ltd.) 65.2 g
A sintered body was prepared in the same manner as in Example 1 except that (Comparative Example 5) and (Comparative Example 5) were used, and the crystal phase of the product was subjected to an X-ray diffraction test (CuKα ray) in the same manner as in Example 1. I tried to identify it by this.
【００３１】Ｍ元素のイオン半径と得られた焼結体の組
成とその結晶構造の関係を表３に示す。Table 3 shows the relationship between the ionic radius of the M element and the composition of the obtained sintered body and its crystal structure.
【００３２】本比較例４及び比較例５においては、同定
できない未知相が現れた。この結晶相は恐らく、Ｂａx
Ｍy ＯZ （ｘ，ｙおよびｚは実数，ＭはＮｄ又はＬａ）
系化合物であると推察される。また、炭酸バリウムと酸
化ネオジム又は炭酸バリウムと酸化ランタンの残存が認
められた。In Comparative Examples 4 and 5, an unidentifiable unknown phase appeared. This crystalline phase is probably Ba x
M y O Z (x, y and z are real numbers, M is Nd or La)
It is presumed to be a system compound. In addition, residual barium carbonate and neodymium oxide or barium carbonate and lanthanum oxide were observed.
【００３３】[0033]
【表３】 [Table 3]
【００３４】[0034]
【表４】 [Table 4]
【００３５】表２及び表４に示された結果より、実施例
１〜３の化合物では、３５０℃付近の酸素欠陥の秩序−
無秩序転移点を境に、導電率が２．５桁以上向上するの
に対して、比較例２及び比較例３の化合物では、導電率
の向上は１桁程度にとどまり、比較例１の化合物におい
ては、もはや、飛躍的な導電率の向上は認められないこ
とが分かる。From the results shown in Tables 2 and 4, in the compounds of Examples 1 to 3, the order of oxygen defects near 350 ° C.
The conductivity is improved by 2.5 digits or more at the disordered transition point, whereas the conductivity of the compounds of Comparative Examples 2 and 3 is improved by only about 1 digit, and the conductivity of the compound of Comparative Example 1 is reduced. It can be seen that no dramatic increase in conductivity is observed any longer.
Claims (3)
Ｍは、酸素６配位を仮定した場合のイオン半径が０．９
０〜０．９７オングストロ−ムである３価の金属元素か
ら選ばれる一種又は二種以上の金属元素）であるブラウ
ンミラ−ライト関連化合物からなることを特徴とする固
体電解質。1. The composition has the general formula: Ba 3 M 4 O 9 (wherein
M has an ionic radius of 0.9 assuming oxygen 6 coordination.
1. A solid electrolyte comprising a brown-milarite-related compound which is one or more metal elements selected from trivalent metal elements of 0 to 0.97 angstrom.
Ｍは、酸素６配位を仮定した場合のイオン半径が０．９
０〜０．９７オングストロ−ムである３価の金属元素か
ら選ばれる一種又は二種以上の金属元素）で表され、そ
の結晶相が六方晶単一相である焼結体よりなることを特
徴とする固体電解質。2. The composition has the general formula: Ba 3 M 4 O 9 (wherein
M has an ionic radius of 0.9 assuming oxygen 6 coordination.
One or two or more metal elements selected from trivalent metal elements of 0 to 0.97 angstrom), and the crystal phase thereof is a hexagonal single phase. And solid electrolyte.
サマリウムからなる群から選ばれる一種又は二種以上の
金属元素であることを特徴とする請求項１又は２に記載
の固体電解質。3. The solid electrolyte according to claim 1, wherein M is one or more metal elements selected from the group consisting of dysprosium, gadolinium and samarium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7342746A JPH09183657A (en) | 1995-12-28 | 1995-12-28 | Solid electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7342746A JPH09183657A (en) | 1995-12-28 | 1995-12-28 | Solid electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09183657A true JPH09183657A (en) | 1997-07-15 |
Family
ID=18356177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7342746A Pending JPH09183657A (en) | 1995-12-28 | 1995-12-28 | Solid electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09183657A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372382A (en) * | 2019-07-15 | 2019-10-25 | 惠州学院 | A kind of Ba3Gd4O9Preparation method |
| JP2020070203A (en) * | 2018-10-30 | 2020-05-07 | 学校法人神奈川大学 | Acid hydroxide, method for producing the same, proton conductor, and catalyst carrier |
| JPWO2020153485A1 (en) * | 2019-01-24 | 2020-07-30 |
-
1995
- 1995-12-28 JP JP7342746A patent/JPH09183657A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020070203A (en) * | 2018-10-30 | 2020-05-07 | 学校法人神奈川大学 | Acid hydroxide, method for producing the same, proton conductor, and catalyst carrier |
| JPWO2020153485A1 (en) * | 2019-01-24 | 2020-07-30 | ||
| US12586804B2 (en) | 2019-01-24 | 2026-03-24 | Institute Of Science Tokyo | Solid electrolyte, electrolyte layer and battery |
| CN110372382A (en) * | 2019-07-15 | 2019-10-25 | 惠州学院 | A kind of Ba3Gd4O9Preparation method |
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