JPH08119732A - Production of solid electrolyte - Google Patents
Production of solid electrolyteInfo
- Publication number
- JPH08119732A JPH08119732A JP6264784A JP26478494A JPH08119732A JP H08119732 A JPH08119732 A JP H08119732A JP 6264784 A JP6264784 A JP 6264784A JP 26478494 A JP26478494 A JP 26478494A JP H08119732 A JPH08119732 A JP H08119732A
- Authority
- JP
- Japan
- Prior art keywords
- zro
- rare earth
- zro2
- solid electrolyte
- solid
- 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.)
- Granted
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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、固体電解質型燃料電池
セルや、酸素センサなどに用いられる固体電解質の製造
方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a solid electrolyte type fuel cell, a solid electrolyte used for an oxygen sensor and the like.
【０００２】[0002]
【従来技術】ＺｒＯ2 を主体としてなる固体電解質は、
燃料電池セルや酸素センサ等をはじめ、各種の電気化学
セルに使用されている。これらの固体電解質は、ＺｒＯ
2 に対して安定化剤としてＹ2 Ｏ3 、ＢａＯ、ＣａＯな
どの安定化剤を固溶させたものが一般的に使用されてお
り、ＺｒＯ2 に対する焼結助剤としては、Ａｌ2 Ｏ3や
ＳｉＯ2 などが主として用いられている。 2. Description of the Related Art A solid electrolyte mainly composed of ZrO 2 is
It is used in various electrochemical cells including fuel cells and oxygen sensors. These solid electrolytes are ZrO
A solid solution of a stabilizer such as Y 2 O 3 , BaO, or CaO is generally used for 2 as a stabilizer, and Al 2 O 3 is used as a sintering aid for ZrO 2 . And SiO 2 are mainly used.
【０００３】例えば、固体電解質型燃料電池において
は、円筒型と平板型の２種類の燃料電池について知られ
ているが、平板型燃料電池セルの場合、図１に示すよう
に、Ｙ2 Ｏ3 あるいはＹｂ2 Ｏ3 で安定化したＺｒＯ2
からなる固体電解質１の一方の面に多孔性のＬａの２０
原子％のＣａで、あるいは１５原子％のＳｒで置換した
ＬａＭｎＯ3 系材料からなる空気極２が形成され、他方
の面に多孔性のＮｉ−ＺｒＯ2 （Ｙ2 Ｏ3 含有）サーメ
ットの燃料極３が設けられている。単セルの接続にはセ
パレータ４と呼ばれる緻密質のＭｇＯやＣａＯを添加し
たＬａＣｒＯ3 固溶体が用いられる。発電は、セルの空
気極側に空気（酸素）、燃料極側に燃料（水素）を供給
して１０００〜１０５０℃の温度で行われる。For example, in solid oxide fuel cells, two types of fuel cells, cylindrical type and flat type, are known. In the case of flat type fuel cells, as shown in FIG. 1, Y 2 O 3 is used. Or ZrO 2 stabilized with Yb 2 O 3
On one surface of the solid electrolyte 1 made of
An air electrode 2 made of a LaMnO 3 -based material substituted with atomic% Ca or 15 atomic% Sr is formed, and a porous Ni-ZrO 2 (Y 2 O 3 -containing) cermet fuel electrode is formed on the other surface. 3 is provided. For connecting the single cells, a solid solution of LaCrO 3 to which a dense MgO or CaO is added, which is called a separator 4, is used. Power generation is performed at a temperature of 1000 to 1050 ° C. by supplying air (oxygen) to the air electrode side of the cell and fuel (hydrogen) to the fuel electrode side.
【０００４】[0004]
【発明が解決しようとする問題点】しかしながら、図１
に示した構造において、固体電解質は１００〜３００μ
ｍの厚みのＹ2 Ｏ3 あるいはＹｂ2 Ｏ3 で安定化したＺ
ｒＯ2 からなる固体電解質が用いられているが、従来の
電解質粉末はかなり焼結性が改善されているものの、燃
料電池セルでは上述のように厚みが薄いために十分に緻
密化しているとは言いがたく特に結晶が粒成長しやす
く、その結果、少量のガスのリークが起こり本来の発電
性能を示さないという問題があった。However, the problem shown in FIG.
In the structure shown in FIG.
Z stabilized with m 2 of Y 2 O 3 or Yb 2 O 3
A solid electrolyte made of rO 2 is used. Although the conventional electrolyte powder has considerably improved sinterability, it is said that the fuel cell is sufficiently densified because of its thin thickness as described above. It is difficult to say that crystals are particularly likely to grow grains, and as a result, a small amount of gas leaks and the original power generation performance is not exhibited.
【０００５】しかも、従来からＺｒＯ2 に対する焼結助
剤として用いられるＡｌ2 Ｏ3 やＳｉＯ2 などは、焼結
体中においてＺｒＯ2 結晶粒子の粒界に析出し電解質の
電気伝導度を低下させたり、燃料電池セルにおいては運
転中に空気極中に拡散して空気極の電極性能を劣化させ
るなどの弊害があった。[0005] Moreover, the like Al 2 O 3, SiO 2 conventionally used as a sintering aid for ZrO 2, reduces the electrical conductivity of the ZrO 2 electrolyte deposited on the grain boundaries of crystal grains in the sintered body In the fuel cell, there is an adverse effect such as diffusion into the air electrode during operation and deterioration of the electrode performance of the air electrode.
【０００６】[0006]
【問題点を解決するための手段】本発明者らは、安定化
ＺｒＯ2 からなる固体電解質の焼結性を改善すべく検討
を重ねた結果、安定化剤を含有するＺｒＯ2 固溶体粉末
に対して、Ｙおよび希土類元素から選ばれる少なくとも
１種の元素の酸化物を添加（以下、後添加物ということ
もある。）してこれを焼成すると、ＺｒＯ2 の粒成長が
抑制される結果、焼結体の緻密化が促進されることを知
見した。[Means for Solving the Problems] As a result of repeated studies to improve the sinterability of a solid electrolyte made of stabilized ZrO 2 , the present inventors have found that a ZrO 2 solid solution powder containing a stabilizer is used. Then, when an oxide of at least one element selected from Y and rare earth elements is added (hereinafter sometimes referred to as a post-additive) and baked, the grain growth of ZrO 2 is suppressed. It was found that densification of the union is promoted.
【０００７】即ち、本発明の固体電解質の製造方法は、
Ｙおよび希土類元素から選ばれる少なくとも１種の酸化
物からなる安定化剤を固溶したＺｒＯ2 粉末に後添加物
としてＹおよび希土類元素から選ばれる少なくとも１種
を含む化合物を酸化物換算で０．０１〜１０モル％添加
混合し、この混合物を成形した後、１２００〜１７００
℃の酸化性雰囲気中で焼成することを特徴とするもので
ある。That is, the method for producing a solid electrolyte of the present invention comprises:
A compound containing at least one selected from Y and a rare earth element as an after-addition is added to ZrO 2 powder in which a stabilizer made of at least one oxide selected from Y and a rare earth element is solid-dissolved in terms of oxide. After adding and mixing 01 to 10 mol% and molding this mixture, 1200 to 1700
It is characterized by firing in an oxidizing atmosphere at ℃.
【０００８】以下、本発明を詳述する。本発明による固
体電解質の製造方法によれば、出発原料としてまず、安
定化剤を固溶するＺｒＯ2 粉末を作製する。このＺｒＯ
2 粉末中に固溶させる安定化剤としてはＹおよび希土類
元素から選ばれる少なくとも１種の元素の酸化物が挙げ
られる。これら安定化剤は、ＺｒＯ2 固溶体粉末中に１
〜２０モル％の割合で含有され、その結果、ＺｒＯ2 は
一部または全部安定化され、結晶相としては一部安定化
された場合には、正方晶または立方晶を主体とし場合に
よりわずかな単斜晶が含まれる場合もある。また、完全
安定化された場合には立方晶ＺｒＯ2 のみから構成され
る。The present invention will be described in detail below. According to the method for producing a solid electrolyte according to the present invention, as a starting material, first, ZrO 2 powder in which a stabilizer is solid-dissolved is produced. This ZrO
2 As the stabilizer to be dissolved in the powder, an oxide of at least one element selected from Y and rare earth elements can be mentioned. These stabilizers were added to the ZrO 2 solid solution powder at 1%.
When ZrO 2 is partially or wholly stabilized and partially stabilized as a crystal phase, it is mainly tetragonal or cubic and may be slightly contained. It may also contain monoclinic crystals. Further, when completely stabilized, it is composed only of cubic ZrO 2 .
【０００９】このＺｒＯ2 固溶体粉末は、ＺｒＯ2 粉末
に所定の割合でＹ、Ｙｂ、Ｓｃ、Ｅｒ、Ｎｄ、Ｄｙ、Ｃ
ｅ、ＳｍおよびＧｄの群から選ばれる少なくとも１種の
元素の酸化物を安定化剤として添加混合したものを１０
００〜１７００℃の酸化性雰囲気中で熱処理して固相反
応することにより得ることができる。その他、例えばＹ
Ｃｌ3 、ＺｒＯＣｌ2 などを用いた周知の共沈法、凍結
乾燥法などによって作製されたものも使用できる。な
お、安定化剤固溶ＺｒＯ2 粉末は、原料粉末として平均
粒径が０．１〜５μｍ程度になるように所望により粉砕
などにより粒度調整することが望ましい。This ZrO 2 solid solution powder contains Y, Yb, Sc, Er, Nd, Dy and C at a predetermined ratio to the ZrO 2 powder.
and a mixture of oxides of at least one element selected from the group consisting of e, Sm and Gd as a stabilizer,
It can be obtained by heat treatment in an oxidizing atmosphere at 00 to 1700 ° C. and solid-phase reaction. Others, for example Y
Those produced by a well-known coprecipitation method using Cl 3 , ZrOCl 2, or the like, a freeze-drying method, or the like can also be used. The stabilizer-dissolved ZrO 2 powder is preferably pulverized or the like so that the average particle diameter of the raw material powder is about 0.1 to 5 μm.
【００１０】本発明によれば、このＺｒＯ2 固溶体粉末
に対して、さらにＹおよび希土類元素から選ばれる少な
くとも１種の元素を含む化合物を０．０１〜１０モル
％、特に１〜５モル％の割合で添加することが重要であ
る。この添加物の量が０．０１モル％より少ないと焼結
性の改善効果がなく、１０モル％を越えると固体電解質
の電気伝導度が低下し電解質として使用できない。この
後添加物であるＹおよび希土類元素から選ばれる少なく
とも１種の元素を含む化合物としては、酸化物粉末の他
に硝酸塩、硫酸塩、酢酸塩などの形態で添加することも
できるが、ＺｒＯ2 の粒成長抑制効果は、この添加物が
均一に分散しているほど効果的であることから、望まし
くは、溶液状態で添加することが望ましい。硝酸塩、硫
酸塩を使用する場合には、一度焼成前に４００〜１００
０℃で熱処理して分解し酸化物を形成することもでき
る。According to the present invention, a compound containing at least one element selected from Y and rare earth elements is added to the ZrO 2 solid solution powder in an amount of 0.01 to 10 mol%, particularly 1 to 5 mol%. It is important to add in proportion. If the amount of this additive is less than 0.01 mol%, the effect of improving the sinterability will not be obtained. As the compound containing at least one element selected from Y and a rare earth element, which is an additive after this, it is possible to add in the form of nitrate, sulfate, acetate, etc. in addition to the oxide powder, but ZrO 2 The effect of suppressing grain growth is more effective when the additive is uniformly dispersed. Therefore, it is desirable to add the additive in a solution state. When using nitrates or sulfates, 400 to 100 before firing once.
It can also be decomposed by heat treatment at 0 ° C. to form an oxide.
【００１１】なお、ＺｒＯ2 固溶体に添加されるＹおよ
び希土類元素から選ばれる少なくとも１種の元素を含む
化合物として酸化物粉末を用いる場合には、平均粒径と
して０．０１〜３μｍ、特に０．１〜１μｍが好まし
い。これは、平均粒径が上記範囲を逸脱すると、ＺｒＯ
2 に対する粒成長を抑制し、焼結性を高める効果が小さ
いためである。When an oxide powder is used as the compound containing at least one element selected from Y and rare earth elements added to the ZrO 2 solid solution, the average particle size is 0.01 to 3 μm, and particularly 0.1. 1 to 1 μm is preferable. This is because when the average particle size deviates from the above range, ZrO
This is because the effect of suppressing grain growth and increasing sinterability for 2 is small.
【００１２】また、本発明品においては、Ａｌ、Ｓｉは
酸化物換算でそれぞれ３重量％以下、特に１重量％以下
に制御することが望ましい。Ａｌ、Ｓｉ量が上記割合よ
り多いと粒成長が著しく、Ｙおよび希土類元素の添加効
果が小さくなるためである。In the product of the present invention, Al and Si are preferably controlled to 3% by weight or less, especially 1% by weight or less in terms of oxide. This is because if the amount of Al and Si is larger than the above ratio, grain growth is remarkable and the effect of adding Y and the rare earth element is reduced.
【００１３】次に、上記のように添加物を添加した混合
物を所望の成形手段、例えば、金型プレス，冷間静水圧
プレス，押出成形、ドクターブレード法等により任意の
形状に成形した後、その成形体を大気などの酸化性雰囲
気中で１２００〜１７００℃、特に１３００〜１６００
℃の温度で焼成することにより固体電解質を作製するこ
とができる。Next, the mixture to which the additives are added as described above is molded into a desired shape by a desired molding means, for example, a mold press, a cold isostatic press, an extrusion molding, a doctor blade method or the like, The molded product is 1200 to 1700 ° C., particularly 1300 to 1600, in an oxidizing atmosphere such as air.
A solid electrolyte can be produced by firing at a temperature of ° C.
【００１４】本発明において用いられる後添加物の成分
としてはＹおよび希土類元素としては、Ｓｃ、Ｌａ、Ｃ
ｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｇｄ、Ｄｙ、Ｅｒ、Ｙｂが挙げ
られる。Y is used as a component of the post additive used in the present invention, and Sc, La and C are used as rare earth elements.
Examples thereof include e, Pr, Nd, Sm, Gd, Dy, Er and Yb.
【００１５】最終的に得られる固体電解質中のＹおよび
希土類元素から選ばれる少なくとも１種の元素の酸化物
の全含有量は２〜２０モル％が適当である。これは２モ
ル％より少ないか、２０モル％より多いと電気伝導度が
小さくなり電解質としての利用ができなくなるためであ
る。The total content of oxides of at least one element selected from Y and rare earth elements in the finally obtained solid electrolyte is preferably 2 to 20 mol%. This is because if it is less than 2 mol% or more than 20 mol%, the electric conductivity becomes small and it cannot be used as an electrolyte.
【００１６】本発明の固体電解質は、図１に示したよう
な燃料電池セルに有用である。燃料電池において使用さ
れる場合、固体電解質は緻密質であることが重要であ
り、気孔率として１％以下、特に０．５％以下であるこ
とが望ましい。The solid electrolyte of the present invention is useful for a fuel cell as shown in FIG. When used in a fuel cell, it is important that the solid electrolyte be dense, and the porosity is preferably 1% or less, particularly 0.5% or less.
【００１７】また、燃料電池セルを作製する場合、固体
電解質は、厚みが１００〜３００μｍ程度のシートとし
て使用される場合が多いため、それ自体の強度が要求さ
れる。この強度の点から固体電解質のＺｒＯ2 を平均結
晶粒径は０．１〜２０μｍ、特に１〜１０μｍ、さらに
は２〜５μｍであることが望ましい。In the case of producing a fuel cell, the solid electrolyte is often used as a sheet having a thickness of about 100 to 300 μm, and therefore the strength of itself is required. From the viewpoint of this strength, the average crystal grain size of ZrO 2 of the solid electrolyte is preferably 0.1 to 20 μm, particularly 1 to 10 μm, and further preferably 2 to 5 μm.
【００１８】なお、本発明における固体電解質において
は、焼成条件等によりＺｒＯ2 固溶体に後添加したＹ、
Ｙｂ等がＺｒＯ2 中に完全に固溶せずに一部Ｙ2 Ｏ3 、
Ｙｂ2 Ｏ3 の酸化物として副相を形成する場合がある
が、その量は少ないために電気伝導などに影響を与える
ことはない。In the solid electrolyte according to the present invention, Y added afterwards to the ZrO 2 solid solution due to firing conditions and the like,
Yb or the like does not completely form a solid solution in ZrO 2 and a part of Y 2 O 3 ,
A subphase may be formed as an oxide of Yb 2 O 3 , but since the amount thereof is small, it does not affect electric conduction or the like.
【００１９】[0019]
【作用】本発明によれば、ＺｒＯ2 固溶体の焼結助剤と
して、ＺｒＯ2 の安定化であるＹおよび希土類元素から
選ばれる少なくとも１種を添加すると、これらの添加物
がＺｒＯ2 結晶内に固溶するまでＺｒＯ2 の粒成長が起
こらず、焼結のみが進行して緻密化が促進されることを
見いだした。この理由については、定かではないが、お
そらくこれらの添加物が焼結中に粒界に存在し粒界エネ
ルギーを低下させ粒成長を抑制するためと考えられ、そ
の結果、焼結のみが進行し緻密化が促進されるものと考
えられる。According to the present invention, when at least one selected from Y which is a stabilizer of ZrO 2 and a rare earth element is added as a sintering aid of the ZrO 2 solid solution, these additives are incorporated into the ZrO 2 crystal. It was found that ZrO 2 grain growth did not occur until a solid solution was formed, and only sintering proceeded to promote densification. The reason for this is not clear, but it is considered that these additives are present at the grain boundaries during sintering and lower the grain boundary energy to suppress grain growth, and as a result, only sintering proceeds. It is considered that densification is promoted.
【００２０】従来のＺｒＯ2 の焼結助剤としては、Ａｌ
2 Ｏ3 やＳｉＯ2 などが主として用いられるが、これら
の添加物は粒界に析出し電解質の電気伝導度を低下させ
たり、燃料電池セルにおいては運転中に空気極中に拡散
して空気極の電極性能を劣化させるなどの弊害があっ
た。As a conventional sintering aid for ZrO 2 , Al is used.
2 O 3 and SiO 2 are mainly used, but these additives are deposited on the grain boundaries to reduce the electrical conductivity of the electrolyte, and in fuel cells, they diffuse into the air electrode during operation and the air electrode There was an adverse effect such as deterioration of the electrode performance of.
【００２１】それに対して、本発明によれば、添加物は
焼結後はほとんど安定化ＺｒＯ2 中の固溶されるため
に、粒界に析出し電気伝導度を劣化させたり、空気極中
に拡散して電極性能を低下させることがない。また、本
発明による固体電解質は、粒成長を抑制しているため、
結晶粒子が小さく、後添加物を全く添加しない場合に比
較して高強度であるという特長も有する。On the other hand, according to the present invention, since the additive is almost solid-soluted in the stabilized ZrO 2 after the sintering, it is precipitated at the grain boundary and deteriorates the electric conductivity, or in the air electrode. There is no possibility that the electrode performance will be deteriorated by diffusing into. Further, since the solid electrolyte according to the present invention suppresses grain growth,
It also has the features of small crystal grains and higher strength than when no post-additives are added.
【００２２】[0022]
実施例１ 市販の純度９９．９％以上、平均粒径が０．５〜０．８
μｍのＹ2 Ｏ3 を１０モル％固溶する安定化ＺｒＯ2 粉
末、Ｙｂ2 Ｏ3 を１０モル％固溶する安定化ＺｒＯ2 お
よびＳｃ2 Ｏ3 を１４モル％固溶する安定化ＺｒＯ2 粉
末をそれぞれ準備した。これにＬａ、Ｙ、Ｙｂ、Ｓｃ、
Ｅｒ、Ｎｄ、Ｓｍ、Ｃｅ、Ｇｄの少なくとも１種の元素
を含む硝酸塩、あるいは平均粒径が０．５〜１μｍの酸
化物粉末、酢酸塩、硫酸塩、および塩化物を酸化物換算
で表１に示す量で添加し、メタノール溶液中でＺｒＯ2
ボールを用いて１０時間混合した。この後、混合粉末を
乾燥し、５×５×４０ｍｍの大きさに成形して１５００
℃で３時間大気中で焼成した。Example 1 Commercial purity of 99.9% or more, average particle size of 0.5 to 0.8
μm of Y 2 O 3 10 mol% solid solution stabilized ZrO 2 powder, Yb 2 O 3 stabilized solid solution 10 mol% ZrO 2 and Sc 2 O 3 of 14 mol% solid solution stabilized ZrO 2 Each powder was prepared. La, Y, Yb, Sc,
A nitrate containing at least one element of Er, Nd, Sm, Ce, and Gd, or an oxide powder having an average particle size of 0.5 to 1 μm, acetate, sulfate, and chloride in terms of oxide is shown in Table 1. And added in an amount of ZrO 2 in a methanol solution.
Mix using a ball for 10 hours. After this, the mixed powder is dried and molded into a size of 5 × 5 × 40 mm and 1500
Firing was performed in the air for 3 hours at ℃.
【００２３】また、比較のために、硝酸塩等を何ら含ま
ない、上記各種の安定化ＺｒＯ2 粉末を用いて上記と同
様な条件で焼成した。For comparison, various types of stabilized ZrO 2 powders containing no nitrate or the like were used and fired under the same conditions as above.
【００２４】得られた各焼結体に対してアルキメデス法
により開気孔率の測定と、大気中１０００℃における電
気伝導度を直流４端子法により測定した。The open porosity of each of the obtained sintered bodies was measured by the Archimedes method, and the electric conductivity at 1000 ° C. in the atmosphere was measured by the DC 4-terminal method.
【００２５】[0025]
【表１】 [Table 1]
【００２６】表１によれば、安定化剤を固溶し完全安定
化されたＺｒＯ2 粉末をそのまま成形し焼成した試料Ｎ
o.１、２３では、いずれも開気孔率が２％を越えるもの
であり、緻密性に欠けることがわかる。これに対して、
後添加物としてＹおよび希土類元素から選ばれる少なく
とも１種を含む化合物を加えることにより、焼結性が改
善され、開気孔率１％以下の高緻密体を有し、さらに１
０００℃における電気伝導度も０．１０ｓ／ｃｍ以上が
達成された。According to Table 1, Sample N was obtained by directly molding and firing ZrO 2 powder in which a stabilizer was solid-solved and completely stabilized.
In both Nos. 1 and 23, the open porosity exceeds 2% in both cases, and it can be seen that the compactness is lacking. On the contrary,
By adding a compound containing at least one selected from Y and rare earth elements as a post additive, the sinterability is improved, and a highly dense body having an open porosity of 1% or less is further added.
The electric conductivity at 000 ° C. was also 0.10 s / cm or more.
【００２７】しかし、添加物の量が０．０１モル％より
少ない試料Ｎo.２では焼結性の向上が見られず、１０モ
ル％を越える試料Ｎo.１０では電気伝導度が低下したた
め、この添加物の量は０．０１〜１０モル％が適当であ
ることがわかった。However, in sample No. 2 containing less than 0.01 mol% of the additive, no improvement in sinterability was observed, and in sample No. 10 exceeding 10 mol%, the electrical conductivity decreased, so It has been found that an appropriate amount of additive is 0.01 to 10 mol%.
【００２８】また、本発明品では、後添加物のない試料
に対して結晶粒子径が小さく粒成長が抑制されているこ
とがわかる。また、本発明品は結晶粒子径が小さいため
強度も高いものであった。Further, in the product of the present invention, it is found that the crystal grain size is small and the grain growth is suppressed as compared with the sample without the post-addition. Further, the product of the present invention has a small crystal grain size and thus has high strength.
【００２９】[0029]
【発明の効果】以上詳述したように、本発明の固体電解
質の製造方法によれば、ＺｒＯ2 の粒成長を抑制し、し
かも隣接する電極などに悪影響を及ぼすことなく、焼結
体の緻密化を促進することができる。従って、燃料電池
セルや酸素センサなどの電気化学装置に用いた場合、こ
れらの装置の信頼性を高めることができる。As described above in detail, according to the method for producing a solid electrolyte of the present invention, it is possible to suppress the grain growth of ZrO 2 and to prevent the adjacent electrodes from being adversely affected by the compactness of the sintered body. Can be promoted. Therefore, when used in electrochemical devices such as fuel cells and oxygen sensors, the reliability of these devices can be increased.
【図１】平板型燃料電池セルの構造を説明するための概
略図である。FIG. 1 is a schematic diagram for explaining the structure of a flat-plate fuel cell unit.
１ 固体電解質 ２ 空気極 ３ 燃料極 ４ セパレータ 1 solid electrolyte 2 air electrode 3 fuel electrode 4 separator
Claims (1)
も１種の酸化物からなる安定化剤を固溶したＺｒＯ2 粉
末にＹおよび希土類元素から選ばれる少なくとも１種を
含む化合物を酸化物換算で０．０１〜１０モル％の割合
で添加混合し、この混合物を成形後、１２００〜１７０
０℃の酸化性雰囲気中で焼成することを特徴とする固体
電解質の製造方法。1. A ZrO 2 powder in which a stabilizer composed of at least one oxide selected from Y and rare earth elements is solid-dissolved, and a compound containing at least one selected from Y and rare earth elements is converted to oxide. Add and mix in a proportion of 0.01 to 10 mol%, and after molding this mixture, 1200 to 170
A method for producing a solid electrolyte, which comprises firing in an oxidizing atmosphere at 0 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26478494A JP3260988B2 (en) | 1994-10-28 | 1994-10-28 | Method for producing solid electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26478494A JP3260988B2 (en) | 1994-10-28 | 1994-10-28 | Method for producing solid electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08119732A true JPH08119732A (en) | 1996-05-14 |
| JP3260988B2 JP3260988B2 (en) | 2002-02-25 |
Family
ID=17408154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26478494A Expired - Fee Related JP3260988B2 (en) | 1994-10-28 | 1994-10-28 | Method for producing solid electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3260988B2 (en) |
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| JPH1097859A (en) * | 1996-09-24 | 1998-04-14 | Mitsubishi Heavy Ind Ltd | Solid electrolyte type electrochemical cell and manufacture thereof |
| JP2002134121A (en) * | 2000-10-23 | 2002-05-10 | Toho Gas Co Ltd | Solid electrolyte fuel cell |
| JP2002145663A (en) * | 2000-11-02 | 2002-05-22 | Nippon Shokubai Co Ltd | Zirconia-based ceramic and method of producing the same |
| JP2002316870A (en) * | 2001-04-19 | 2002-10-31 | Nitsukatoo:Kk | Member for heat treatment consisting of zirconia sintered compact |
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| JP2005082429A (en) * | 2003-09-08 | 2005-03-31 | Nitsukatoo:Kk | Zirconia-made heat treating member |
| JP2005259556A (en) * | 2004-03-12 | 2005-09-22 | Nissan Motor Co Ltd | Solid electrolyte and its manufacturing method |
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- 1994-10-28 JP JP26478494A patent/JP3260988B2/en not_active Expired - Fee Related
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|---|---|---|---|---|
| JPH1097859A (en) * | 1996-09-24 | 1998-04-14 | Mitsubishi Heavy Ind Ltd | Solid electrolyte type electrochemical cell and manufacture thereof |
| JP2002134121A (en) * | 2000-10-23 | 2002-05-10 | Toho Gas Co Ltd | Solid electrolyte fuel cell |
| JP2002145663A (en) * | 2000-11-02 | 2002-05-22 | Nippon Shokubai Co Ltd | Zirconia-based ceramic and method of producing the same |
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| JP2005259556A (en) * | 2004-03-12 | 2005-09-22 | Nissan Motor Co Ltd | Solid electrolyte and its manufacturing method |
| JP2013505884A (en) * | 2009-09-10 | 2013-02-21 | 中国砿業大学（北京） | Composite sintering aid and method for producing nanocrystalline ceramic at low temperature using the same |
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| WO2012105580A1 (en) * | 2011-01-31 | 2012-08-09 | Toto株式会社 | Solid oxide fuel cell |
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