TWI809118B - Solid electrolyte and solid electrolyte junction - Google Patents

Solid electrolyte and solid electrolyte junction Download PDF

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TWI809118B
TWI809118B TW108119471A TW108119471A TWI809118B TW I809118 B TWI809118 B TW I809118B TW 108119471 A TW108119471 A TW 108119471A TW 108119471 A TW108119471 A TW 108119471A TW I809118 B TWI809118 B TW I809118B
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solid electrolyte
oxide
intermediate layer
layer
formula
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TW202000628A (en
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井手慎吾
大山旬春
八木輝明
田平泰規
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日商三井金屬鑛業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • 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

Abstract

本發明之課題在於提供能夠降低具備固體電解質之裝置之電阻之固體電解質。本發明之固體電解質包含具有氧化物離子傳導性之磷灰石型複合氧化物，且藉由X射線繞射測定所獲得之002之峰強度I002 相對於004之峰強度I004 之比即I002 /I004 之值為0.3以上0.8以下。固體電解質較佳為配向於c軸。亦揭示上述固體電解質與金屬氧化物之中間層或金屬電極層接合而成之固體電解質接合體。上述金屬氧化物較佳為包含含有選自由釤、釔、釓及鑭所組成之群中之一種或兩種以上元素之氧化鈰。An object of the present invention is to provide a solid electrolyte capable of reducing the resistance of a device having a solid electrolyte. The solid electrolyte of the present invention includes an apatite-type composite oxide having oxide ion conductivity, and the ratio of the peak intensity I 002 of 002 to the peak intensity I 004 of 004 obtained by X-ray diffraction measurement is I The value of 002 /I 004 is not less than 0.3 and not more than 0.8. The solid electrolyte is preferably aligned to the c-axis. Also disclosed is a solid electrolyte assembly in which the above-mentioned solid electrolyte is bonded to an intermediate layer of a metal oxide or a metal electrode layer. The aforementioned metal oxide is preferably cerium oxide containing one or two or more elements selected from the group consisting of samarium, yttrium, gadolinium and lanthanum.

Description

固體電解質及固體電解質接合體Solid electrolyte and solid electrolyte junction

本發明係關於一種固體電解質及固體電解質接合體。本發明之固體電解質及固體電解質接合體用於利用其氧化物離子傳導性之各種領域。The present invention relates to a solid electrolyte and a solid electrolyte assembly. The solid electrolyte and solid electrolyte assembly of the present invention are used in various fields utilizing the ion conductivity of the oxide.

已知有各種氧化物離子傳導性固體電解質。此種固體電解質例如作為透氧元件、燃料電池之電解質、及氣體感測器等用於各種領域。例如專利文獻1中記載有一種於陽極側電極與陰極側電極之間插裝有包含磷灰石型複合氧化物之固體電解質之電解質、電極接合體。於陰極側電極與固體電解質之間，插裝有氧化物離子傳導顯示出各向同性之中間層。中間層包含摻雜有釤、釔、釓或鑭之氧化鈰。固體電解質包含Lax Si6 O1.5X ＋ 12 (8≦X≦10)。該文獻中記載：藉由該電解質、電極接合體，固體氧化物型燃料電池之發電性能提高。 [先前技術文獻] [專利文獻]Various oxide ion conductive solid electrolytes are known. Such a solid electrolyte is used in various fields such as an oxygen permeable element, an electrolyte of a fuel cell, and a gas sensor. For example, Patent Document 1 describes an electrolyte and an electrode assembly in which a solid electrolyte containing an apatite-type composite oxide is interposed between an anode-side electrode and a cathode-side electrode. Between the cathode side electrode and the solid electrolyte, an intermediate layer showing isotropic oxide ion conduction is inserted. The intermediate layer comprises cerium oxide doped with samarium, yttrium, gadolinium or lanthanum. The solid electrolyte contains La x Si 6 O 1.5X + 12 (8≦X≦10). This document describes that the power generation performance of the solid oxide fuel cell is improved by the electrolyte and the electrode assembly. [Prior Art Document] [Patent Document]

[專利文獻1]日本專利特開2013-51101號公報[Patent Document 1] Japanese Patent Laid-Open No. 2013-51101

如專利文獻1所記載，雖揭示有各種利用氧化物離子傳導性之固體電解質之裝置，但於以裝置整體進行評價之情形時，不能說充分地發揮了固體電解質原本具有之氧化物離子傳導性。尤其，即便於固體電解質本身之氧化物離子傳導性較高之情形時，亦存在固體電解質與電極之界面之電阻變高，作為裝置整體之電阻變高之情形。As described in Patent Document 1, although various devices using solid electrolytes with oxide ion conductivity are disclosed, it cannot be said that the original oxide ion conductivity of solid electrolytes is fully utilized when evaluating the device as a whole. . In particular, even when the oxide ion conductivity of the solid electrolyte itself is high, the resistance at the interface between the solid electrolyte and the electrodes may become high, and the resistance of the device as a whole may become high.

因此，本發明之課題在於提供一種能夠降低具備固體電解質之裝置之電阻之固體電解質及具備該固體電解質之固體電解質接合體。Therefore, an object of the present invention is to provide a solid electrolyte capable of reducing the resistance of a device including the solid electrolyte, and a solid electrolyte assembly including the solid electrolyte.

為了解決上述課題，本發明者經過認真研究，結果發現藉由將具有特定之結晶結構之磷灰石型複合氧化物用作固體電解質能夠解決上述課題。本發明係基於該見解而完成者，藉由提供一種固體電解質而解決上述課題，該固體電解質包含具有氧化物離子傳導性之磷灰石型複合氧化物，且藉由X射線繞射測定所獲得之002之峰強度I002 相對於004之峰強度I004 之比即I002 /I004 之值為0.3以上0.8以下。In order to solve the above-mentioned problems, the inventors of the present invention conducted earnest studies, and as a result, found that the above-mentioned problems can be solved by using an apatite-type composite oxide having a specific crystal structure as a solid electrolyte. The present invention was completed based on this knowledge, and solves the above-mentioned problems by providing a solid electrolyte comprising an apatite-type composite oxide having oxide ion conductivity and obtained by X-ray diffraction measurement. The ratio of the peak intensity I 002 of 002 to the peak intensity I 004 of 004, that is, the value of I 002 /I 004 is 0.3 to 0.8.

又，本發明提供一種上述固體電解質與金屬氧化物之中間層或金屬電極層接合而成之固體電解質接合體。Also, the present invention provides a solid electrolyte assembly in which the above-mentioned solid electrolyte is bonded to an intermediate layer of a metal oxide or a metal electrode layer.

以下，對本發明基於其較佳之實施形態進行說明。本發明之固體電解質包含具有氧化物離子傳導性之磷灰石型複合氧化物。固體電解質係氧化物離子成為載子之導電體。Hereinafter, the present invention will be described based on its preferred embodiments. The solid electrolyte of the present invention includes an apatite-type composite oxide having oxide ion conductivity. A solid electrolyte is a conductor in which oxide ions become carriers.

作為磷灰石型複合氧化物，例如可列舉包含鑭及矽之複合氧化物。作為該磷灰石型複合氧化物，含有作為三價元素之鑭(La)、作為四價元素之矽(Si)、及氧(O)，其組成為以Lax Si6 O1.5x ＋ 12 (x表示8以上10以下之數)表示者，就氧化物離子傳導性高之方面而言較佳。該磷灰石型複合氧化物之最佳之組成為La9.33 Si6 O26 。該複合氧化物例如可按照日本專利特開2013-51101號公報中記載之方法製造。As an apatite type composite oxide, the composite oxide containing lanthanum and silicon is mentioned, for example. This apatite-type composite oxide contains lanthanum (La) as a trivalent element, silicon (Si) as a tetravalent element, and oxygen (O), and its composition is La x Si 6 O 1.5x + 12 (x represents a number from 8 to 10) is preferable in terms of high oxide ion conductivity. The optimum composition of the apatite type composite oxide is La 9.33 Si 6 O 26 . This composite oxide can be produced, for example, according to the method described in JP-A-2013-51101.

作為磷灰石型複合氧化物之另一例，可列舉通式(1)：A9.33 ＋ x [T6.00-y My ]O26.0+z 所示之複合氧化物。該複合氧化物亦係具有磷灰石型結構者。式中之A係選自由La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Yb、Lu、Be、Mg、Ca、Sr及Ba所組成之群中之一種或兩種以上元素。式中之T係包含Si或者Ge或兩者之元素。式中之M係選自由Mg、Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Ga、Zr、Ta、Nb、B、Ge、Zn、Sn、W及Mo所組成之群中之一種或兩種以上元素。就提高c軸配向性之觀點而言，M較佳為選自由B、Ge及Zn所組成之群中之一種或兩種以上元素。As another example of the apatite-type composite oxide, a composite oxide represented by the general formula (1): A 9.33 + x [T 6.00-y M y ]O 26.0+z can be cited. This composite oxide also has an apatite structure. A in the formula is selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Be, Mg, Ca, Sr and Ba one or more elements. T in the formula contains elements of Si or Ge or both. M in the formula is selected from the group consisting of Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Ga, Zr, Ta, Nb, B, Ge, Zn, Sn, W and Mo one or more elements. From the viewpoint of improving c-axis alignment, M is preferably one or two or more elements selected from the group consisting of B, Ge, and Zn.

就提高配向度及氧化物離子傳導性之觀點而言，式中之x較佳為-1.33以上1.50以下，進而佳為0.00以上0.70以下，更佳為0.45以上0.65以下。就填埋磷灰石型晶格中之T元素位置之觀點而言，式中之y較佳為0.00以上3.00以下，進而佳為0.40以上2.00以下，更佳為0.40以上1.00以下。就保持磷灰石型晶格內之電中性之觀點而言，式中之z較佳為-5.00以上5.20以下，進而佳為-2.00以上1.50以下，更佳為-1.00以上1.00以下。From the viewpoint of improving the degree of alignment and oxide ion conductivity, x in the formula is preferably -1.33 to 1.50, more preferably 0.00 to 0.70, more preferably 0.45 to 0.65. From the viewpoint of filling the T element position in the apatite-type lattice, y in the formula is preferably from 0.00 to 3.00, more preferably from 0.40 to 2.00, and more preferably from 0.40 to 1.00. From the viewpoint of maintaining electrical neutrality in the apatite lattice, z in the formula is preferably -5.00 to 5.20, more preferably -2.00 to 1.50, and more preferably -1.00 to 1.00.

於上述式中，A之莫耳數相對於T之莫耳數之比率，換言之，上述式中之(9.33＋x)/(6.00－y)就保持磷灰石型晶格中之空間佔有率之觀點而言，較佳為1.33以上3.61以下，進而佳為1.40以上3.00以下，更佳為1.50以上2.00以下。In the above formula, the ratio of the mole number of A to the mole number of T, in other words, (9.33+x)/(6.00-y) in the above formula maintains the ratio of the space occupancy rate in the apatite lattice. From a viewpoint, it is preferably not less than 1.33 and not more than 3.61, more preferably not less than 1.40 and not more than 3.00, more preferably not less than 1.50 and not more than 2.00.

若使用上述通式(1)所示之複合氧化物中A為鑭之複合氧化物、即La9.33 ＋ x [T6.00-y My ]O26.0+z 所示之複合氧化物，則就氧化物離子傳導性進一步提高之觀點而言較佳。作為La9.33 ＋ x [T6.00-y My ]O26.0+z 所示之複合氧化物之具體例，可列舉：La9.33+x (Si4.70 B1.30 )O26.0+z 、La9.33+x (Si4.70 Ge1.30 )O26.0+z 、La9.33+x (Si4.70 Zn1.30 )O26.0+z 、La9.33+x (Si4.70 W1.30 )O26.0+z 、La9.33+x (Si4.70 Sn1.30 )O26.0+x 、La9.33+x (Ge4.70 B1.30 )O26.0+z 等。上述通式(1)所示之複合氧化物例如可按照US2018/183068A1中記載之方法製造。If A is a composite oxide of lanthanum in the composite oxide represented by the above general formula (1), that is, a composite oxide represented by La 9.33 + x [T 6.00-y My ] O 26.0+z , then the oxidation It is preferable from the viewpoint of further improving ion conductivity. Specific examples of the composite oxide represented by La 9.33 + x [T 6.00-y My ] O 26.0+z include: La 9.33+x (Si 4.70 B 1.30 )O 26.0+z , La 9.33+x ( Si 4.70 Ge 1.30 )O 26.0+z , La 9.33+x (Si 4.70 Zn 1.30 )O 26.0+z , La 9.33+x (Si 4.70 W 1.30 )O 26.0 +z , La 9.33+x (Si 4.70 Sn 1.30 ) O 26.0+x , La 9.33+x (Ge 4.70 B 1.30 )O 26.0+z , etc. The composite oxide represented by the above general formula (1) can be produced, for example, according to the method described in US2018/183068A1.

於使用上述任一者作為磷灰石型複合氧化物之情形時，就能夠有效地降低包含本發明之固體電解質之裝置之電阻之方面而言，該複合氧化物較佳為包含鑭。又，於使用任一磷灰石型複合氧化物之情形時，該複合氧化物較佳為配向於c軸。配向於c軸係指於磷灰石型複合氧化物為多晶體之情形時，結晶軸沿著c軸對齊。進而，於磷灰石型複合氧化物以單晶存在時，能夠使其c軸方向與裝置中之氧化物離子之傳導方向一致。In the case of using any of the above as the apatite-type composite oxide, the composite oxide preferably contains lanthanum in terms of being able to effectively reduce the resistance of a device including the solid electrolyte of the present invention. Also, when any apatite-type composite oxide is used, it is preferable that the composite oxide is aligned on the c-axis. Aligning to the c-axis means that when the apatite-type composite oxide is polycrystalline, the crystallographic axes are aligned along the c-axis. Furthermore, when the apatite-type composite oxide exists as a single crystal, the c-axis direction can be aligned with the conduction direction of oxide ions in the device.

磷灰石型複合氧化物具有如下特徵之一：於對其進行X射線繞射測定時，藉由該測定而獲得之002之峰強度I002 相對於004之峰強度I004 之比即I002 /I004 之值為0.3以上0.8以下。至此，強烈地配向於c軸之磷灰石型複合氧化物若對其進行X射線繞射測定，則存在00x(x表示2以上之偶數)以外之繞射峰強度非常小、定量解析困難之課題。但，本發明者得出002及004之繞射峰值之強度比強烈地反映了缺損部位之量之見解，進而發現，該強度比處於特定範圍之磷灰石型複合氧化物與電極層之界面電阻變低，從而使作為裝置整體之電阻降低。尤其於磷灰石型複合氧化物包含鑭之情形時，若該複合氧化物維持磷灰石型之結晶結構並且鑭缺損，為了保持電荷之平衡，結構中之氧亦缺損。本發明者認為：若產生氧缺損，則氧化物離子容易移動而氧化物離子之傳導性提高，甚至該複合氧化物與電極層之界面電阻進一步變低。又，關於鑭以外之A，認為由於在磷灰石型複合氧化物中容易進入與鑭相同之結晶部位，故表現出與上述相同之機構。如此，本發明係由於固體電解質本身之結晶結構，而並非由於與固體電解質接合之中間層或電極層而提高氧化物離子傳導性。The apatite-type composite oxide has one of the following characteristics: when it is measured by X-ray diffraction, the ratio of the peak intensity I 002 of 002 to the peak intensity I 004 of 004 obtained by the measurement is I 002 The value of / I004 is not less than 0.3 and not more than 0.8. So far, if X-ray diffraction measurement is performed on apatite-type composite oxides that are strongly aligned to the c-axis, the intensity of diffraction peaks other than 00x (x represents an even number greater than 2) is very small, and quantitative analysis is difficult. topic. However, the present inventors found that the intensity ratio of the diffraction peaks of 002 and 004 strongly reflects the amount of the defect, and further found that the interface between the apatite-type composite oxide and the electrode layer where the intensity ratio is in a specific range The resistance becomes lower, thereby reducing the resistance of the device as a whole. Especially when the apatite-type composite oxide contains lanthanum, if the composite oxide maintains the apatite-type crystal structure and lanthanum is deficient, oxygen in the structure is also deficient in order to maintain charge balance. The inventors of the present invention believe that if oxygen deficiency occurs, the oxide ions move easily, the conductivity of the oxide ions increases, and the interface resistance between the composite oxide and the electrode layer further decreases. Also, A other than lanthanum is considered to exhibit the same mechanism as above because it easily enters the same crystal site as lanthanum in the apatite-type composite oxide. Thus, the present invention improves oxide ion conductivity due to the crystalline structure of the solid electrolyte itself, not due to the intermediate layer or electrode layer bonded to the solid electrolyte.

磷灰石型複合氧化物中之缺損部位之量越多，I002 相對於I004 之比之值越小，磷灰石型複合氧化物與電極層之界面電阻越低。就該觀點而言，I002 相對於I004 之比之值較佳為0.5以上0.8以下，進而佳為0.5以上0.75以下。The more defect sites in the apatite composite oxide, the smaller the ratio of I 002 to I 004 , and the lower the interface resistance between the apatite composite oxide and the electrode layer. From this point of view, the value of the ratio of I 002 to I 004 is preferably from 0.5 to 0.8, more preferably from 0.5 to 0.75.

I002 及I004 之值使用X射線繞射法測定。詳細而言，可使用點收斂型X射線聚光鏡(CMF光學系統)、及0維檢測器測定。本發明中言及之X射線繞射之峰強度係指積分強度。The values of I 002 and I 004 were determined using X-ray diffraction method. Specifically, it can be measured using a point-converging X-ray condenser (CMF optical system) and a 0-dimensional detector. The peak intensity of X-ray diffraction referred to in the present invention refers to the integrated intensity.

關於該X射線繞射之峰強度，為了更準確地測定磷灰石型結晶結構中之缺損部位之量，選定獲得更高之X射線繞射強度之002與004之峰強度比作為指標。再者，磷灰石型結晶結構中之002與004之X射線繞射之峰位置可根據公知之結晶資料庫等唯一地確定。Regarding the peak intensity of X-ray diffraction, in order to more accurately measure the amount of defects in the apatite crystal structure, the peak intensity ratio of 002 and 004, which obtains higher X-ray diffraction intensity, was selected as an index. Furthermore, the X-ray diffraction peak positions of 002 and 004 in the apatite crystal structure can be uniquely determined based on known crystal databases and the like.

為了使I002 相對於I004 之比之值滿足上述範圍，較佳為於磷灰石型複合氧化物形成缺損部位。本發明者之研究結果表明：例如形成與磷灰石型複合氧化物鄰接之不同之組成之膜，並對該膜進行退火，藉此自結晶結構去除構成元素、特別是鑭，以此將有利於形成缺損部位。於此情形時，於保持磷灰石型結晶結構之狀態下，需要去除鑭等構成元素。為了此目的，將鑭能夠擴散或者能夠固溶鑭之膜(以下亦稱為「La吸收膜」)積層於磷灰石型複合氧化物之表面。而且，較佳為藉由於700℃以上之高溫進行退火，使磷灰石型複合氧化物中之鑭擴散或固溶於La吸收膜，獲得缺損鑭之磷灰石型複合氧化物。其後，La吸收膜亦可藉由規定之方法去除。In order to make the ratio of I 002 to I 004 satisfy the above range, it is preferable to form a defect in the apatite-type composite oxide. As a result of research by the inventors of the present invention, it has been found that, for example, forming a film of a different composition adjacent to an apatite-type composite oxide and annealing the film can remove constituent elements, especially lanthanum, from the crystal structure, which is advantageous. at the site of the defect. In this case, it is necessary to remove constituent elements such as lanthanum while maintaining the apatite crystal structure. For this purpose, a film capable of diffusing or dissolving lanthanum (hereinafter also referred to as "La absorbing film") is laminated on the surface of the apatite-type composite oxide. Furthermore, it is preferable to anneal at a high temperature of 700° C. or higher to diffuse or dissolve lanthanum in the apatite-type composite oxide in the La absorption film, thereby obtaining a lanthanum-deficient apatite-type composite oxide. Thereafter, the La absorbing film can also be removed by a predetermined method.

本發明之固體電解質根據其具體用途可直接使用，或者可於與其他構件組合之裝置之狀態下使用。圖1表示此種裝置之一例。圖1所示之裝置係具備本發明之固體電解質之固體電解質接合體10。以下，對該固體電解質接合體10進行說明。The solid electrolyte of the present invention can be used directly according to its specific use, or can be used in the state of a device combined with other components. Fig. 1 shows an example of such a device. The device shown in FIG. 1 is a solid electrolyte assembly 10 including the solid electrolyte of the present invention. Hereinafter, the solid electrolyte assembly 10 will be described.

如圖1所示，固體電解質接合體10具備包含上述固體電解質之層(以下稱為「固體電解質層」)11。於固體電解質層11之一面接合有與該固體電解質層11相接而積層之中間層12。於圖1所示之實施形態中，固體電解質層11與中間層12直接相接，兩者間未介隔其他層。中間層12包含具有氧化物離子傳導性及電子傳導性之材料。As shown in FIG. 1 , a solid electrolyte assembly 10 includes a layer (hereinafter referred to as “solid electrolyte layer”) 11 containing the above-mentioned solid electrolyte. An intermediate layer 12 laminated in contact with the solid electrolyte layer 11 is bonded to one surface of the solid electrolyte layer 11 . In the embodiment shown in FIG. 1 , the solid electrolyte layer 11 is in direct contact with the intermediate layer 12 without intervening other layers. The intermediate layer 12 includes a material having oxide ion conductivity and electron conductivity.

就有效地降低固體電解質接合體10之電阻之觀點而言，固體電解質層11之厚度較佳為10 nm以上1000 μm以下，進而佳為50 nm以上700 μm以下，更佳為100 nm以上500 μm以下。該固體電解質層11之厚度例如可使用觸針式輪廓儀、游標卡尺或電子顯微鏡測定。From the viewpoint of effectively reducing the resistance of the solid electrolyte assembly 10, the thickness of the solid electrolyte layer 11 is preferably from 10 nm to 1000 μm, more preferably from 50 nm to 700 μm, more preferably from 100 nm to 500 μm the following. The thickness of the solid electrolyte layer 11 can be measured using, for example, a stylus profiler, a vernier caliper, or an electron microscope.

固體電解質接合體10如圖1所示，亦可具有接合於固體電解質層11之2個面中與配置有中間層12之面為相反側之面之金屬電極層13。固體電解質層11、中間層12及金屬電極層13以此種順序配置，藉此，構成包含固體電解質接合體10之裝置20。於圖1所示之實施形態中，固體電解質層11與金屬電極層13直接相接，兩者間未介隔其他層。As shown in FIG. 1 , the solid electrolyte assembly 10 may have the metal electrode layer 13 bonded to the surface opposite to the surface on which the intermediate layer 12 is disposed, of the two surfaces of the solid electrolyte layer 11 . The solid electrolyte layer 11 , the intermediate layer 12 , and the metal electrode layer 13 are arranged in this order, thereby forming a device 20 including the solid electrolyte assembly 10 . In the embodiment shown in FIG. 1 , the solid electrolyte layer 11 is in direct contact with the metal electrode layer 13 , and no other layers are interposed between them.

中間層12包含金屬氧化物而構成。中間層12僅包含金屬氧化物，或包含金屬氧化物及其他物質。中間層12以順利地進行與固體電解質層11之間之氧化物離子之授受為目的而形成。根據本實施形態，由於使用具有上述特定之結晶結構之固體電解質作為固體電解質層11，故無論中間層12之種類如何，都能夠降低固體電解質層11與中間層12之間之界面電阻，能夠更順利地進行氧化物離子之授受。The intermediate layer 12 is composed of a metal oxide. The intermediate layer 12 contains only metal oxide, or contains metal oxide and other substances. The intermediate layer 12 is formed for the purpose of smoothly transferring oxide ions to and from the solid electrolyte layer 11 . According to this embodiment, since the solid electrolyte having the above-mentioned specific crystal structure is used as the solid electrolyte layer 11, regardless of the type of the intermediate layer 12, the interface resistance between the solid electrolyte layer 11 and the intermediate layer 12 can be reduced, and more The transfer and reception of oxide ions is carried out smoothly.

中間層12可較佳地使用包含金屬氧化物、且具有氧化物離子傳導性者。作為中間層12，例如可使用包含選自由釤、釔、釓及鑭所組成之群中之一種或兩種以上元素(以下，為方便起見，亦將該等元素稱為「摻雜元素」)之氧化鈰。於此情形時，摻雜元素之含量以M/(M＋Ce)×100表示 (M表示摻雜元素之莫耳數)，較佳為0.1莫耳%以上0.5莫耳%以下，更佳為0.15莫耳%以上0.4莫耳%以下，又更佳為0.2莫耳%以上0.3莫耳%以下。The intermediate layer 12 can preferably use a metal oxide that has oxide ion conductivity. As the intermediate layer 12, for example, one or two or more elements selected from the group consisting of samarium, yttrium, gadolinium, and lanthanum can be used (hereinafter, for convenience, these elements are also referred to as "doping elements"). ) of cerium oxide. In this case, the content of the doping element is represented by M/(M+Ce)×100 (M represents the number of moles of the doping element), preferably 0.1 mol% to 0.5 mol%, more preferably 0.15 mol mol% to 0.4 mol%, more preferably 0.2 mol% to 0.3 mol%.

亦可使用鉍之氧化物作為中間層12。作為鉍之氧化物，例如可列舉氧化鉍(III)或鉍與其他金屬元素之複合氧化物。作為其他金屬元素，例如可列舉一種以上稀土類元素。作為稀土類元素，例如可列舉鑭、釓、釔、鉺、鐿、鏑等。尤其，就能夠有效地降低固體電解質層11與中間層12之間之電阻之觀點而言，中間層12較佳為包含鉍與鑭、釓或釔之複合氧化物。進而，該複合氧化物較佳為以(Lnm Bin )2 O3 表示。式中，Ln表示稀土類元素。m與n之和為1，n＞0。又，m較佳為0.1以上0.4以下。Bismuth oxide can also be used as the intermediate layer 12 . As an oxide of bismuth, bismuth (III) oxide or the composite oxide of bismuth and another metal element is mentioned, for example. As other metal elements, for example, one or more kinds of rare earth elements can be cited. Examples of rare earth elements include lanthanum, gadolinium, yttrium, erbium, ytterbium, and dysprosium. In particular, the intermediate layer 12 is preferably a composite oxide containing bismuth and lanthanum, gadolinium, or yttrium from the viewpoint of being able to effectively reduce the resistance between the solid electrolyte layer 11 and the intermediate layer 12 . Furthermore, the composite oxide is preferably represented by (Ln m Bin ) 2 O 3 . In the formula, Ln represents a rare earth element. The sum of m and n is 1, and n>0. Also, m is preferably from 0.1 to 0.4.

亦可使用具有氧化物離子傳導性及電子傳導性之混合傳導體作為中間層12。混合傳導體係具有氧化物離子傳導性及電子傳導性之2種傳導性、即混合傳導性之物質。尤其，就於固體電解質層11與中間層12之界面中謀求相對於配向方向正交之面之晶格匹配之觀點而言，構成中間層12之材料較佳為鈣鈦礦型氧化物。尤其，於構成固體電解質層11之材料係上述通式(1)所示者之情形時，若構成中間層12之材料為鈣鈦礦型氧化物，則能夠始終良好地謀求上述晶格匹配。A mixed conductor having oxide ion conductivity and electron conductivity can also be used as the intermediate layer 12 . The mixed conductivity system is a substance having two kinds of conductivities of oxide ion conductivity and electron conductivity, that is, mixed conductivity. In particular, the material constituting the intermediate layer 12 is preferably a perovskite-type oxide from the viewpoint of achieving lattice matching on the plane perpendicular to the alignment direction at the interface between the solid electrolyte layer 11 and the intermediate layer 12 . In particular, when the material constituting the solid electrolyte layer 11 is represented by the above-mentioned general formula (1), if the material constituting the intermediate layer 12 is a perovskite-type oxide, the above-mentioned lattice matching can always be achieved satisfactorily.

尤其，就更進一步提高氧化物離子傳導性之觀點而言，較佳為使用通式(2)：ABO3 所示者作為構成中間層12之材料。式中，A較佳為使用例如選自La、Sr、Ba及Ca中之一種或兩種以上金屬元素，尤佳之金屬元素係La及Sr中之至少一種。B為過渡金屬元素，較佳為使用選自Co、Ni、Mn、Cr、Ti、Fe、Cu中之一種或兩種以上金屬元素，尤佳之金屬元素係Co及Ni中之至少一種。特別是通式(2)所示之材料較佳為包含La、Sr、Co及Ni之複合氧化物。In particular, from the viewpoint of further improving the ion conductivity of the oxide, it is preferable to use the material represented by the general formula (2): ABO 3 as the material constituting the intermediate layer 12 . In the formula, A is preferably one or two or more metal elements selected from La, Sr, Ba, and Ca, and a particularly preferable metal element is at least one of La and Sr. B is a transition metal element, preferably one or two or more metal elements selected from Co, Ni, Mn, Cr, Ti, Fe, Cu, especially at least one of Co and Ni. In particular, the material represented by the general formula (2) is preferably a composite oxide containing La, Sr, Co, and Ni.

通式(2)所示之複合氧化物中之尤佳者係La0.6 Sr0.4 Co0.9 Ni0.1 O3 － δ 所示者。 Among the composite oxides represented by the general formula (2), those represented by La 0.6 Sr 0.4 Co 0.9 Ni 0.1 O 3 -δ are particularly preferable.

包含通式(2)所示之複合氧化物之中間層12例如可使用各種薄膜形成法形成於固體電解質層11之一面。作為薄膜形成法，可列舉物理氣相蒸鍍法或化學氣相蒸鍍法等，若使用該等中之物理氣相蒸鍍法，則能夠始終更好地形成中間層12。物理氣相蒸鍍法中，尤其較佳為使用PLD(Pulsed Laser Deposition，脈衝激光沈積)法。The intermediate layer 12 including the composite oxide represented by the general formula (2) can be formed on one side of the solid electrolyte layer 11 using various thin film forming methods, for example. As a thin film forming method, a physical vapor deposition method, a chemical vapor deposition method, etc. are mentioned, and the intermediate layer 12 can always be formed better by using the physical vapor deposition method among these. Among the physical vapor deposition methods, it is particularly preferable to use a PLD (Pulsed Laser Deposition, pulsed laser deposition) method.

即便構成中間層12之材料為上述材料中之任一者，就降低界面電阻之觀點而言，使構成固體電解質層11之材料與構成中間層12之材料均沿著固體電解質層11與中間層12之積層方向單軸配向較為有效。為了使構成固體電解質層11之材料與構成中間層12之材料沿著上述積層方向均單軸配向，例如，只要一面將成為基板之固體電解質層11加熱至規定溫度，一面於控制氧分壓之環境下利用物理氣相蒸鍍法或化學氣相蒸鍍法等於固體電解質層11上形成中間層12之薄膜，且使其局部地磊晶生長即可。又，亦可使用原子層沈積法(ALD，atomic layer deposition)，於固體電解質層11上形成中間層12之單軸配向薄膜。但，並不限定於該等方法。Even if the material constituting the intermediate layer 12 is any of the above-mentioned materials, in terms of reducing the interface resistance, the material constituting the solid electrolyte layer 11 and the material constituting the intermediate layer 12 are all along the solid electrolyte layer 11 and the intermediate layer. The uniaxial alignment in the lamination direction of 12 is more effective. In order to make the material constituting the solid electrolyte layer 11 and the material constituting the intermediate layer 12 uniaxially aligned along the above lamination direction, for example, it is only necessary to heat the solid electrolyte layer 11 as the substrate to a predetermined temperature on one side and control the partial pressure of oxygen on the other hand. Under the circumstances, the thin film of the intermediate layer 12 can be formed on the solid electrolyte layer 11 by physical vapor deposition or chemical vapor deposition, and the thin film of the intermediate layer 12 can be locally epitaxially grown. In addition, atomic layer deposition (ALD, atomic layer deposition) can also be used to form a uniaxially aligned thin film of the intermediate layer 12 on the solid electrolyte layer 11 . However, it is not limited to these methods.

構成固體電解質層11之材料與構成中間層12之材料是否均單軸配向，可根據接合界面之利用TEM(transmission electron microscopy，穿透式電子顯微鏡)所進行之剖面觀察來判斷。固體電解質層11及中間層12之晶格常數或面間隔可根據藉由一面搖動一面進行X射線繞射測定而獲得之繞射圖案算出。Whether the material constituting the solid electrolyte layer 11 and the material constituting the intermediate layer 12 are uniaxially aligned can be judged by observing the cross-section of the bonding interface using a TEM (transmission electron microscope). The lattice constant and interplanar spacing of the solid electrolyte layer 11 and the intermediate layer 12 can be calculated from the diffraction pattern obtained by performing X-ray diffraction measurement while shaking.

即便構成中間層12之材料為上述材料中之任一者，中間層12只要具有規定厚度，就能夠有效地降低與固體電解質層11之間之電阻。詳細而言，接合於固體電解質層11之中間層12之沿著積層方向之厚度較佳為80 nm以上，進而佳為100 nm以上，更佳為100 nm以上1000 nm以下。中間層12之厚度可藉由觸針式輪廓儀或電子顯微鏡測定。Even if the material constituting the intermediate layer 12 is any of the above-mentioned materials, the resistance between the intermediate layer 12 and the solid electrolyte layer 11 can be effectively reduced as long as the intermediate layer 12 has a predetermined thickness. Specifically, the thickness of the intermediate layer 12 bonded to the solid electrolyte layer 11 along the lamination direction is preferably 80 nm or more, more preferably 100 nm or more, and more preferably 100 nm or more and 1000 nm or less. The thickness of the middle layer 12 can be measured by a stylus profiler or an electron microscope.

就容易形成、且具有觸媒活性較高等優點而言，隔著固體電解質層11而形成於與中間層12為相反側之金屬電極層13較佳為包含鉑族元素而構成。作為鉑族元素，例如可列舉鉑、釕、銠、鈀、鋨及銥等。該等元素可單獨使用一種，或組合兩種以上使用。又，亦可使用包含鉑族元素之金屬陶瓷作為金屬電極層13。The metal electrode layer 13 formed on the opposite side to the intermediate layer 12 through the solid electrolyte layer 11 is preferably composed of platinum group elements in terms of easy formation and high catalytic activity. Examples of platinum group elements include platinum, ruthenium, rhodium, palladium, osmium, and iridium. These elements may be used alone or in combination of two or more. In addition, a cermet containing a platinum group element can also be used as the metal electrode layer 13 .

圖1所示之實施形態之固體電解質接合體10及裝置20例如可藉由以下所述之方法較佳地製造。首先，利用公知之方法製造固體電解質層11。於製造中，例如可採用日本專利特開2013-51101號公報或US2018/183068A1中記載之方法。The solid electrolyte assembly 10 and the device 20 of the embodiment shown in FIG. 1 can be preferably manufactured by, for example, the method described below. First, solid electrolyte layer 11 is produced by a known method. In production, for example, the method described in JP-A-2013-51101 or US2018/183068A1 can be used.

繼而，於固體電解質層11之2個面中之一者形成中間層12。於中間層12之形成中，可使用各種薄膜形成法。作為薄膜形成法之一，例如可使用上述之PLD法。具體而言，為了使構成固體電解質層11之材料與構成中間層12之材料均沿著該固體電解質層11與中間層12之積層方向單軸配向，使用上述之PLD法，於在固體電解質層11之一面形成中間層12時，將該固體電解質層11加熱至規定溫度即可。就始終更好地進行單軸配向之方面而言，加熱溫度較佳為設定為例如600℃以上700℃以下。Next, the intermediate layer 12 is formed on one of the two surfaces of the solid electrolyte layer 11 . In forming the intermediate layer 12, various thin film forming methods can be used. As one of the thin film forming methods, for example, the above-mentioned PLD method can be used. Specifically, in order to uniaxially align the material constituting the solid electrolyte layer 11 and the material constituting the intermediate layer 12 along the stacking direction of the solid electrolyte layer 11 and the intermediate layer 12, the above-mentioned PLD method is used to form When the intermediate layer 12 is formed on one side of the solid electrolyte layer 11, it is only necessary to heat the solid electrolyte layer 11 to a predetermined temperature. The heating temperature is preferably set to, for example, 600° C. or higher and 700° C. or lower from the viewpoint of performing uniaxial alignment better all the time.

以此方式形成中間層12後，於固體電解質層11之與中間層12之形成面為相反側之面形成金屬電極層13。於金屬電極層13之形成中，例如使用包含鉑族金屬之粒子之膏。將該膏塗佈於固體電解質層11之表面形成塗膜，藉由對該塗膜進行焙燒而形成包含多孔質體之電極。焙燒條件可設為溫度600℃以上、時間30分鐘以上120分鐘以下。環境可設為大氣等含氧環境。After the intermediate layer 12 is formed in this manner, the metal electrode layer 13 is formed on the surface of the solid electrolyte layer 11 opposite to the surface on which the intermediate layer 12 is formed. In forming the metal electrode layer 13, for example, a paste containing particles of a platinum group metal is used. This paste is applied on the surface of the solid electrolyte layer 11 to form a coating film, and the coating film is fired to form an electrode including a porous body. The firing conditions can be set at a temperature of 600° C. or higher and a time of 30 minutes or more and 120 minutes or less. The environment may be an oxygen-containing environment such as air.

利用以上方法獲得目標之固體電解質接合體10及裝置20。以此方式獲得之裝置20利用其較高之氧化物離子傳導性，較佳地用作例如以透氧元件、氧感測器為代表之各種氣體感測器、水蒸氣電解或固體電解質型燃料電池等。無論將裝置20用於何種用途，將中間層12用作陰極、即用作產生氧氣之還原反應之極較為有利。例如於將裝置20用作透氧元件之情形時，將金屬電極層13連接於直流電源之陽極，並將中間層12連接於直流電源之陰極，對中間層12與金屬電極層13之間施加規定直流電壓。藉此，於中間層12側，氧接收電子而生成氧化物離子。生成之氧化物離子於固體電解質層11中移動，到達金屬電極層13。到達金屬電極層13之氧化物離子釋出電子而成為氧氣。藉由此種反應，固體電解質層11能夠使中間層12側之環境中所含之氧氣通過固體電解質層11向金屬電極層13側透過。再者，根據需要，亦可於中間層12之表面及金屬電極層13之表面中之至少一者形成包含鉑等導電性材料之集電層。The target solid electrolyte assembly 10 and device 20 were obtained by the above method. The device 20 obtained in this way is preferably used as various gas sensors represented by oxygen permeable elements, oxygen sensors, water vapor electrolysis or solid electrolyte type fuels by utilizing its higher oxide ion conductivity. battery etc. Regardless of the application for which the device 20 is used, it is advantageous to use the intermediate layer 12 as the cathode, ie as the pole of the reduction reaction that produces oxygen. For example, when the device 20 is used as an oxygen-permeable element, the metal electrode layer 13 is connected to the anode of the DC power supply, and the intermediate layer 12 is connected to the cathode of the DC power supply. Specifies the DC voltage. As a result, oxygen receives electrons on the side of the intermediate layer 12 to generate oxide ions. The generated oxide ions move in the solid electrolyte layer 11 and reach the metal electrode layer 13 . The oxide ions reaching the metal electrode layer 13 release electrons and become oxygen gas. Through this reaction, the solid electrolyte layer 11 allows oxygen contained in the environment on the intermediate layer 12 side to pass through the solid electrolyte layer 11 to the metal electrode layer 13 side. Furthermore, if necessary, a collector layer made of a conductive material such as platinum may be formed on at least one of the surface of the intermediate layer 12 and the surface of the metal electrode layer 13 .

施加之電壓就提高氧氣之透過量之觀點而言，較佳為設定為0.1 V以上4.0 V以下。於兩極間施加電壓時，較佳為固體電解質層11之氧化物離子傳導性充分變高。例如氧化物離子傳導性以傳導率表示較佳為1.0×10－ 3 S/cm以上。為了此目的，較佳為將固體電解質層11、或裝置20整體保持於規定溫度。該保持溫度亦取決於固體電解質層11之材質，但通常較佳為設定為300℃以上600℃以下之範圍。藉由於該條件下使用裝置20，能夠使中間層12側之環境中所含之氧氣通過固體電解質層11向金屬電極層13側透過。The applied voltage is preferably set to 0.1 V or more and 4.0 V or less from the viewpoint of increasing the oxygen permeation amount. When a voltage is applied between the two electrodes, it is preferable that the oxide ion conductivity of the solid electrolyte layer 11 becomes sufficiently high. For example, the oxide ion conductivity expressed as conductivity is preferably 1.0× 10 −3 S /cm or more. For this purpose, it is preferable to maintain the solid electrolyte layer 11 or the entire device 20 at a predetermined temperature. This holding temperature also depends on the material of the solid electrolyte layer 11, but it is usually preferably set within a range of 300°C to 600°C. By using the device 20 under this condition, oxygen gas contained in the environment on the intermediate layer 12 side can pass through the solid electrolyte layer 11 to the metal electrode layer 13 side.

於將裝置20亦用作極限電流式氧感測器之情形時，由於在中間層12側生成之氧化物離子經由固體電解質層11向金屬電極層13側移動而產生電流。由於電流值依賴於中間層12側之氧氣濃度，故藉由測定電流值能夠測定中間層12側之氧氣濃度。When the device 20 is also used as a limiting current type oxygen sensor, a current is generated due to oxide ions generated on the intermediate layer 12 side moving to the metal electrode layer 13 side through the solid electrolyte layer 11 . Since the current value depends on the oxygen concentration on the intermediate layer 12 side, the oxygen concentration on the intermediate layer 12 side can be measured by measuring the current value.

以上，對本發明基於其較佳之實施形態進行了說明，但本發明並不限制於上述實施形態。例如於上述實施形態中，僅於固體電解質層11之一面配置中間層12，但亦可取而代之，如圖2所示，固體電解質層11於與中間層12對向之面配置另一中間層12'。於固體電解質層11於與中間層12對向之面配置另一中間層12'之情形時，各中間層12、12'可相同，或者亦可不同。於此情形時，較佳為構成固體電解質層11之材料、構成一中間層12之材料及構成另一中間層12'之材料均沿著該等之積層方向單軸配向。As mentioned above, although this invention was demonstrated based on the preferable embodiment, this invention is not limited to the said embodiment. For example, in the above-mentioned embodiment, the intermediate layer 12 is disposed only on one side of the solid electrolyte layer 11, but it can also be replaced. As shown in FIG. '. When the solid electrolyte layer 11 is provided with another intermediate layer 12 ′ on the surface facing the intermediate layer 12 , the intermediate layers 12 and 12 ′ may be the same or different. In this case, it is preferable that the material constituting the solid electrolyte layer 11, the material constituting the one intermediate layer 12, and the material constituting the other intermediate layer 12' are all uniaxially aligned along the lamination directions.

又，亦可代替於固體電解質層11之各面形成中間層12、12'，如圖3所示，形成金屬電極層13、13'。於此情形時，能夠降低裝置20整體之電阻。各金屬電極層13、13'可相同，或者亦可不同。 實施例In addition, instead of forming intermediate layers 12, 12' on each surface of solid electrolyte layer 11, as shown in FIG. 3, metal electrode layers 13, 13' may be formed. In this case, the resistance of the device 20 as a whole can be reduced. The metal electrode layers 13 and 13' may be the same or different. Example

以下，藉由實施例進一步詳細地對本發明進行說明。然而，本發明之範圍並不限制於上述實施例。只要無特別說明，則「%」係指「質量%」。Hereinafter, the present invention will be described in further detail by means of examples. However, the scope of the present invention is not limited to the above-mentioned embodiments. Unless otherwise specified, "%" means "mass %".

〔實施例1〕 將La2 O3 之粉體與SiO2 之粉體以莫耳比為1：1之方式進行調配，加入乙醇並以球磨機混合。使其混合物乾燥，並以研缽粉碎，使用鉑坩堝於大氣環境下在1650℃焙燒3小時。對其焙燒物加入乙醇並以球磨機粉碎而獲得焙燒粉。將該焙燒粉放入20 mmϕ 之成形器，自一方向加壓而進行單軸成形。進而，於700 MPa進行1分鐘冷均壓加壓(CIP，cold isostatic pressing)而形成顆粒。將該顆粒狀成形體於大氣中、以1600℃加熱3小時，獲得顆粒狀燒結體。將該燒結體用於粉末X射線繞射測定及化學分析，結果確認到具有磷灰石型結晶結構之La2 SiO5 之結構。[Example 1] La 2 O 3 powder and SiO 2 powder were prepared in a molar ratio of 1:1, ethanol was added and mixed with a ball mill. The mixture was dried, pulverized in a mortar, and baked at 1650° C. for 3 hours in an air atmosphere using a platinum crucible. Ethanol was added to the calcined product, and it was pulverized by a ball mill to obtain a calcined powder. Put the calcined powder into a 20 mm ϕ shaper, and press from one direction for uniaxial molding. Furthermore, cold isostatic pressing (CIP, cold isostatic pressing) was performed at 700 MPa for 1 minute to form pellets. This granular molded body was heated at 1600° C. for 3 hours in the air to obtain a granular sintered body. The sintered body was subjected to powder X-ray diffraction measurement and chemical analysis, and as a result, the structure of La 2 SiO 5 having an apatite crystal structure was confirmed.

將所獲得之顆粒800 mg與B2 O3 粉末140 mg放入帶蓋匣缽內。使用電爐將該顆粒及B2 O3 粉末於大氣中以1550℃(爐內環境溫度)加熱50小時。藉由該加熱，於匣缽內產生B2 O3 蒸氣，並且使B2 O3 蒸氣與顆粒反應而獲得目標之固體電解質層11。該固體電解質層11於La9.33 ＋ x [Si6.00 － y By ]O26.0 ＋ z 中，x＝0.50、y＝1.17、z＝0.16，La與Si之莫耳比為2.04。又，藉由游標卡尺測定之厚度為350 μm。以下，將該化合物簡稱為「LSBO」。800 mg of the obtained granules and 140 mg of B 2 O 3 powder were put into a sagger with a lid. The particles and B 2 O 3 powder were heated in the air at 1550° C. (ambient temperature in the furnace) for 50 hours using an electric furnace. By this heating, B 2 O 3 vapor is generated in the sagger, and the B 2 O 3 vapor reacts with the particles to obtain the target solid electrolyte layer 11 . In the solid electrolyte layer 11, in La 9.33 + x [Si 6.00 − y By y ]O 26.0 + z , x=0.50, y=1.17, z=0.16, and the molar ratio of La to Si is 2.04. Also, the thickness measured with a caliper was 350 μm. Hereinafter, this compound is abbreviated as "LSBO".

〔La吸收膜之製造〕 將Bi2 O3 之粉體放入50 mmϕ 之成形器，自一方向加壓而進行單軸成形，繼而進行熱壓燒結。燒結之條件設為氮氣環境、壓力30 MPa、溫度600℃、3小時，獲得濺鍍用靶。使用該靶，藉由高頻濺鍍法，於包含LSBO之固體電解質層11之兩面以300 nm之厚度進行濺鍍。濺鍍之條件係RF輸出為30 W、氬氣之壓力為0.8 Pa。濺鍍結束後，於大氣中、以750℃進行1小時退火。藉由該退火，固體電解質中之La向Bi2 O3 層(La吸收層)側擴散，形成La缺損LSBO。其次，進行自該固體電解質去除吸收有La之層之操作。詳細而言，使用精密研磨裝置，將吸收有La之Bi2 O3 層完全去除。其後，藉由游標卡尺測定之La缺損LSBO之厚度為340 μm。〔Manufacture of La absorbing film〕 Put the powder of Bi 2 O 3 into a 50 mm ϕ shaper, apply pressure from one direction for uniaxial forming, and then perform hot-press sintering. The sintering conditions were set at a nitrogen atmosphere, a pressure of 30 MPa, and a temperature of 600° C. for 3 hours to obtain a target for sputtering. Using this target, sputtering was performed with a thickness of 300 nm on both surfaces of the solid electrolyte layer 11 including LSBO by a high-frequency sputtering method. The conditions of sputtering were that the RF output was 30 W, and the pressure of argon gas was 0.8 Pa. After completion of sputtering, annealing was performed at 750° C. for 1 hour in the air. By this annealing, La in the solid electrolyte diffuses toward the Bi 2 O 3 layer (La absorbing layer), forming La-deficient LSBO. Next, an operation of removing the layer having absorbed La from the solid electrolyte is performed. Specifically, the Bi 2 O 3 layer having absorbed La was completely removed using a precision polishing device. Thereafter, the thickness of the La-deficient LSBO measured by a caliper was 340 μm.

〔實施例2〕 於實施例1中，將La吸收層於800℃進行1小時退火，除此以外，以與實施例1相同之方式製造La缺損LSBO。[Example 2] In Example 1, La-deficient LSBO was produced in the same manner as in Example 1 except that the La absorbing layer was annealed at 800° C. for 1 hour.

〔實施例3〕 於實施例1中，將La吸收層於850℃進行1小時退火，除此以外，以與實施例1相同之方式製造La缺損LSBO。[Example 3] In Example 1, La-deficient LSBO was produced in the same manner as in Example 1 except that the La absorbing layer was annealed at 850° C. for 1 hour.

〔比較例1〕 於實施例1中，不形成La吸收層，因此不進行退火，除此以外，以與實施例1相同之方式製造固體電解質。[Comparative Example 1] In Example 1, a solid electrolyte was produced in the same manner as in Example 1 except that annealing was not performed because the La absorption layer was not formed.

〔評價1〕 對於實施例及比較例中獲得之固體電解質，藉由以下所述之方法進行XRD測定，求出I002 /I004 之值。又，藉由以下所述之方法測定氧化物離子之傳導率。將該等結果示於以下表1。[Evaluation 1] The solid electrolytes obtained in Examples and Comparative Examples were subjected to XRD measurement by the method described below to obtain the value of I 002 /I 004 . Also, the conductivity of oxide ions was measured by the method described below. These results are shown in Table 1 below.

〔XRD測定〕 使用Rigaku股份公司之全自動多目的X射線繞射裝置SmartLab於以下條件下進行測定。 管電壓：40 kV 管電流：30 mA X射線源：CuKα 入射光學元件：共焦鏡(Confocal mirror)(CMF) 入射側狹縫構成：準直器尺寸1.4 mm×1.4 mm 受光側狹縫構成：平行狹縫分析儀0.114 deg、受光狹縫20 mm 檢測器：閃爍計數器 測定範圍：2θ＝20～60 deg 步進寬度：0.01 deg 掃描速度：1 deg/分鐘 解析中使用理學(Rigaku)股份公司之PDXL2。藉由於背底選擇連接端點之直線、於峰形狀選擇分割型擬Voigt函數，進行輪廓擬合而獲得002及004之峰強度(積分強度)。002之峰及004之峰如上所述c軸配向，故係不與其他面之峰重疊之獨立之峰。於在作為裝置設為多層構成之情況下假定之存在與來自其他相之峰重疊之情形時，由於能夠與一般之XRD資料解析同樣地進行峰分解，故能夠得到僅002及004之峰強度。〔XRD measurement〕 The measurement was performed under the following conditions using a fully automatic multi-purpose X-ray diffraction device SmartLab of Rigaku Co., Ltd. Tube voltage: 40 kV Tube current: 30mA X-ray source: CuKα Entrance optics: Confocal mirror (CMF) Incident side slit composition: collimator size 1.4 mm×1.4 mm Light-receiving side slit configuration: Parallel slit analyzer 0.114 deg, light-receiving slit 20 mm Detector: scintillation counter Measuring range: 2θ＝20～60 deg Step width: 0.01 deg Scanning speed: 1 deg/min PDXL2 of Rigaku Co., Ltd. was used for the analysis. The peak intensities (integrated intensities) of 002 and 004 were obtained by contour fitting by selecting a straight line connecting the endpoints for the background and selecting a segmented quasi-Voigt function for the peak shape. The peak of 002 and the peak of 004 are c-axis aligned as described above, so they are independent peaks that do not overlap with peaks of other planes. When it is assumed that peaks from other phases overlap with other phases in the case of a multi-layer structure as a device, only the peak intensities of 002 and 004 can be obtained because the peaks can be decomposed in the same way as in general XRD data analysis.

〔氧化物離子之傳導率之測定〕 於固體電解質之兩面使用濺鍍法製膜150 nm厚之鉑膜而形成電極。將該固體電解質載置於加熱爐中，使加熱爐之溫度變化而進行固體電解質之複阻抗解析。於解析中使用阻抗測定裝置，頻率設為0.1 Hz～32 MHz。根據全電阻成分(晶內電阻＋晶界電阻)求出氧化物離子傳導率(S/cm)。將600℃下之氧化物離子傳導率示於表1。〔Measurement of conductivity of oxide ions〕 Platinum films with a thickness of 150 nm were formed on both sides of the solid electrolyte by sputtering to form electrodes. This solid electrolyte was placed in a heating furnace, and the temperature of the heating furnace was changed to perform complex impedance analysis of the solid electrolyte. An impedance measurement device was used in the analysis, and the frequency was set at 0.1 Hz to 32 MHz. Calculate the oxide ion conductivity (S/cm) from the total resistance component (intragranular resistance + grain boundary resistance). Table 1 shows the oxide ion conductivity at 600°C.

[表1] [Table 1]

由表1所示之結果明確可知，與比較例之固體電解質相比而言，I002 /I004 之值為特定之範圍之各實施例中獲得之固體電解質之傳導率約高5倍以上，氧化物離子傳導性之提高效果較高。It is clear from the results shown in Table 1 that, compared with the solid electrolyte of the comparative example, the conductivity of the solid electrolyte obtained in each example in which the value of I 002 /I 004 is within a specific range is about 5 times higher, The effect of improving the ion conductivity of oxides is high.

〔實施例4〕 於實施例1中獲得之固體電解質之兩面形成包含含有釔之Bi2 O3 之中間層12。於中間層12之形成中，使用藉由以下方法製造之靶。使用該靶於固體電解質之兩面進行濺鍍而形成中間層。形成中間層後，於700℃進行1小時加熱，製造固體電解質接合體10。[Example 4] The intermediate layer 12 made of Bi 2 O 3 containing yttrium was formed on both surfaces of the solid electrolyte obtained in Example 1. In formation of the intermediate layer 12, the target manufactured by the following method was used. Using this target, sputtering was performed on both surfaces of the solid electrolyte to form an intermediate layer. After the intermediate layer was formed, it was heated at 700° C. for 1 hour to manufacture the solid electrolyte assembly 10 .

〔靶之製造〕 調配規定量之Y2 O3 粉體與Bi2 O3 粉體，加入乙醇並以球磨機混合。使該混合物乾燥並以研缽粉碎，使用氧化鋁坩堝，於大氣環境下在700℃焙燒3小時。於該焙燒物中加入乙醇並以行星型球磨機粉碎，獲得焙燒粉末。將該焙燒粉末放入50 mmϕ 之成形器，自一方向加壓而進行單軸成形，之後進行熱壓燒結。燒結之條件設為氮氣環境、壓力30 MPa、溫度600℃、3小時。如此，獲得濺鍍用靶。[Manufacture of target] Prepare predetermined amounts of Y 2 O 3 powder and Bi 2 O 3 powder, add ethanol, and mix with a ball mill. This mixture was dried and pulverized in a mortar, and fired at 700° C. for 3 hours in an air atmosphere using an alumina crucible. Ethanol was added to the calcined product, and it was pulverized by a planetary ball mill to obtain a calcined powder. Put the calcined powder into a 50 mm ϕ shaper, press from one direction for uniaxial molding, and then perform hot-press sintering. The sintering conditions were set as a nitrogen atmosphere, a pressure of 30 MPa, a temperature of 600° C., and 3 hours. In this way, a target for sputtering was obtained.

〔實施例5〕 代替實施例4中使用之靶，使用包含含有釤之氧化鈰之靶。該靶以與實施例4中使用之靶相同之方法製造。使用該靶，藉由與實施例4相同之方法，製造包含含有釤之氧化鈰之中間層12。如此，製造固體電解質接合體10。[Example 5] Instead of the target used in Example 4, a target comprising samarium-containing cerium oxide was used. This target was produced in the same manner as the target used in Example 4. Using this target, by the same method as in Example 4, the intermediate layer 12 containing samarium-containing cerium oxide was produced. In this way, the solid electrolyte assembly 10 was produced.

〔比較例2〕 於比較例1中獲得之固體電解質之兩面形成包含含有釤之氧化鈰之中間層。中間層之形成與實施例5相同。[Comparative Example 2] On both sides of the solid electrolyte obtained in Comparative Example 1, an intermediate layer comprising samarium-containing cerium oxide was formed. The formation of the intermediate layer is the same as in Example 5.

〔電流密度之測定〕 對實施例4及5以及比較例2中獲得之固體電解質接合體測定電阻。測定係於600℃進行。於大氣中對中間層間施加直流電壓1 V，根據所獲得之電流值算出電流密度。將該結果示於表2。〔Measurement of current density〕 The electrical resistance of the solid electrolyte assemblies obtained in Examples 4 and 5 and Comparative Example 2 was measured. The measurement is carried out at 600°C. A DC voltage of 1 V was applied between the intermediate layers in the atmosphere, and the current density was calculated from the obtained current value. The results are shown in Table 2.

[表2] [Table 2]

自表2所示之結果明確可知，於I002 /I004 之值為特定之範圍之固體電解質設置有中間層之固體電解質接合體，與比較例之固體電解質接合體相比，可獲得約7倍以上之高電流密度值。 [產業上之可利用性]From the results shown in Table 2, it can be clearly seen that the solid electrolyte assembly provided with the intermediate layer in the value of I 002 /I 004 within a specific range, compared with the solid electrolyte assembly of the comparative example, can obtain about 7 times the high current density value. [Industrial availability]

根據本發明，提供能夠降低具備固體電解質之裝置之電阻之固體電解質。又，根據本發明，提供電阻低之固體電解質接合體。According to the present invention, a solid electrolyte capable of reducing the resistance of a device including the solid electrolyte is provided. Also, according to the present invention, a solid electrolyte assembly having low electrical resistance is provided.

10‧‧‧固體電解質接合體 11‧‧‧固體電解質層 12‧‧‧中間層 12'‧‧‧中間層 13‧‧‧金屬電極層 13'‧‧‧金屬電極層 20‧‧‧裝置10‧‧‧Solid electrolyte junction 11‧‧‧Solid electrolyte layer 12‧‧‧intermediate layer 12'‧‧‧Middle layer 13‧‧‧Metal electrode layer 13'‧‧‧Metal electrode layer 20‧‧‧Devices

圖1係表示具備本發明之固體電解質之裝置之一實施形態之模式圖。 圖2係表示具備本發明之固體電解質之裝置之另一實施形態之模式圖。 圖3係表示具備本發明之固體電解質之裝置之又一實施形態之模式圖。Fig. 1 is a schematic view showing an embodiment of a device including a solid electrolyte of the present invention. Fig. 2 is a schematic view showing another embodiment of a device including the solid electrolyte of the present invention. Fig. 3 is a schematic view showing still another embodiment of a device including the solid electrolyte of the present invention.

10‧‧‧固體電解質接合體 10‧‧‧Solid electrolyte junction

11‧‧‧固體電解質層 11‧‧‧Solid electrolyte layer

12‧‧‧中間層 12‧‧‧intermediate layer

13‧‧‧金屬電極層 13‧‧‧Metal electrode layer

20‧‧‧裝置 20‧‧‧Devices

Claims (9)

一種固體電解質，其包含具有氧化物離子傳導性之磷灰石型複合氧化物，且藉由X射線繞射測定所獲得之002之峰強度I002相對於004之峰強度I004之比即I002/I004之值為0.3以上0.8以下，上述複合氧化物以通式：A9.33+x[T6.00-yMy]O26.0+z(式中之A係選自由La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Yb、Lu、Be、Mg、Ca、Sr及Ba所組成之群中之一種或兩種以上元素，式中之T係包含Si或者Ge或兩者之元素，式中之M係選自由Mg、Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Ga、Zr、Ta、Nb、B、Ge、Zn、Sn、W及Mo所組成之群中之一種或兩種以上元素)表示，式中之x係-1.33以上1.50以下之數，式中之y係0.40以上2.00以下之數，式中之z係-5.00以上5.20以下之數，且A之莫耳數相對於T之莫耳數之比率為1.33以上3.61以下。 A solid electrolyte comprising an apatite-type composite oxide having oxide ion conductivity, and the ratio of the peak intensity I 002 of 002 to the peak intensity I 004 of 004 obtained by X-ray diffraction measurement is I The value of 002 /I 004 is not less than 0.3 and not more than 0.8. The above-mentioned composite oxide has a general formula: A 9.33+x [T 6.00-y M y ]O 26.0+z (the A in the formula is selected from La, Ce, Pr, One or two or more elements in the group consisting of Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Be, Mg, Ca, Sr and Ba, where T contains Si or Ge or elements of both, M in the formula is selected from Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Ga, Zr, Ta, Nb, B, Ge, Zn, One or two or more elements in the group consisting of Sn, W and Mo) means that x in the formula is a number from -1.33 to 1.50, y in the formula is a number from 0.40 to 2.00, and z in the formula is -A number between 5.00 and 5.20, and the ratio of the molar number of A to the molar number of T is 1.33 to 3.61. 如請求項1之固體電解質，其配向於c軸。 The solid electrolyte according to claim 1, which is aligned on the c-axis. 一種固體電解質接合體，其係如請求項1或2之固體電解質與金屬氧化物之中間層或金屬電極層接合而成。 A solid electrolyte assembly, which is formed by bonding the solid electrolyte according to claim 1 or 2 with an intermediate layer of metal oxide or a metal electrode layer. 如請求項3之固體電解質接合體，其中上述金屬氧化物包含含有選自由釤、釔、釓及鑭所組成之群中之一種或兩種以上元素之氧化鈰。 The solid electrolyte assembly according to claim 3, wherein the metal oxide includes cerium oxide containing one or two or more elements selected from the group consisting of samarium, yttrium, gadolinium, and lanthanum. 如請求項3所述之固體電解質接合體，其中上述金屬氧化物包含鉍之 氧化物。 The solid electrolyte assembly according to claim 3, wherein the metal oxide contains bismuth oxide. 如請求項3之固體電解質接合體，其中上述金屬氧化物包含具有氧化物離子傳導性及電子傳導性之混合傳導體。 The solid electrolyte assembly according to claim 3, wherein the metal oxide includes a mixed conductor having oxide ion conductivity and electron conductivity. 如請求項3至6中任一項之固體電解質接合體，其中於上述固體電解質接合體中與配置有上述中間層或上述電極層之面為相反側之面，配置有與該中間層或該電極層相同或不同之中間層或電極層。 The solid electrolyte assembly according to any one of claims 3 to 6, wherein, on the surface of the solid electrolyte assembly opposite to the surface on which the intermediate layer or the electrode layer is arranged, the intermediate layer or the electrode layer is arranged on the solid electrolyte assembly. An intermediate or electrode layer with the same or different electrode layers. 如請求項3至6中任一項之固體電解質接合體，其用作透氧元件、氣體感測器、水蒸氣電解或固體電解質型燃料電池。 The solid electrolyte assembly according to any one of claims 3 to 6, which is used as an oxygen permeable element, a gas sensor, water vapor electrolysis, or a solid electrolyte fuel cell. 如請求項7之固體電解質接合體，其用作透氧元件、氣體感測器、水蒸氣電解或固體電解質型燃料電池。 The solid electrolyte assembly according to claim 7, which is used as an oxygen permeable element, a gas sensor, water vapor electrolysis or a solid electrolyte fuel cell.
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