JPS63201051A - Proton conductive solid electrolyte - Google Patents
Proton conductive solid electrolyteInfo
- Publication number
- JPS63201051A JPS63201051A JP62028316A JP2831687A JPS63201051A JP S63201051 A JPS63201051 A JP S63201051A JP 62028316 A JP62028316 A JP 62028316A JP 2831687 A JP2831687 A JP 2831687A JP S63201051 A JPS63201051 A JP S63201051A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- oxygen
- conductive solid
- proton conductive
- conductivity
- 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
- 239000007784 solid electrolyte Substances 0.000 title claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052732 germanium Inorganic materials 0.000 claims 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims 1
- 229910052735 hafnium Inorganic materials 0.000 claims 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- -1 interbium Chemical compound 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、高温型プロトン導電性固体電解質に関するも
のである。このようなプロトン導電性固体電解質は、燃
料電池および各種センサ（Ｈｔセンサ、ＮＯｘセンサ、
ＣＯセンサ等）の材料として期待されている。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a high temperature proton conductive solid electrolyte. Such proton conductive solid electrolytes are used in fuel cells and various sensors (Ht sensors, NOx sensors,
It is expected to be used as a material for CO sensors, etc.
従来、高温型プロトン導電性固体電解質として知られて
いる材料は、ストロンチウムとセリウムの酸化物を母体
とし、これに、イツトリウム、スカンジウム、イッテル
ビウム、ネオジム、マグネシウム、プラセオジム及び亜
鉛の少なくとも一種の金属の酸化物を含む材料で構成さ
れていた（特開昭５８−５０４５８号公報）。この様な
固体酸化物の一般式を下に示す。The material conventionally known as a high-temperature proton-conductive solid electrolyte has a matrix of strontium and cerium oxides, and an oxide of at least one of the following metals: yttrium, scandium, ytterbium, neodymium, magnesium, praseodymium, and zinc. (Japanese Unexamined Patent Publication No. 58-50458). The general formula of such a solid oxide is shown below.
５ｒＣｅ＋−ｘ Ｍｘ ０ｓ−ｙ
（ここで、Ｍは、Ｙ、Ｓｃ 、Ｙｂ 、Ｎｄ 、
Ｐｒ 。5rCe+-x Mx 0s-y (here, M is Y, Sc, Yb, Nd,
Pr.
Ｍｇ又はＺｎを示し、Ｘは０．５以下の数値を示し、α
は０から０．５の数値を示す）。Indicates Mg or Zn, X indicates a numerical value of 0.5 or less, α
indicates a numerical value from 0 to 0.5).
この様な酸化物において、４価のＣｅをそれより低イオ
ン価のイオンで置換するため、酸素欠陥が生じ、電荷補
償が行なわれる。下記に、５ｒＣｅＯ。In such an oxide, since the tetravalent Ce is replaced with an ion having a lower valence, oxygen defects are generated and charge compensation is performed. Below, 5rCeO.
にＹｂｚＯｓを添加した場合の例を示す。An example is shown in which YbzOs is added to.
（ここで、ｙｂ’、、は５ｒＣｅＯｓのＣｅの位置に置
換固溶されたｙｂを表わし、ｖｏｏ。は５ｒＣｅ０２中
の０の位置の欠陥（酸素欠陥）を表わし、０゜は５ｒＣ
ｅＯｓ中のＯの位置を占める酸素を表わす。）
このような酸素欠陥に起因して、プロトンが生成し、プ
ロトン導電性が生じるとされている。プロトン生成機構
としては、下記に示す、〔Ｉ〕、および（ＩＩ）のプロ
セスが考えられる。(Here, yb',, represents yb substituted as a solid solution at the Ce position of 5rCeOs, voo. represents a defect (oxygen defect) at the 0 position in 5rCe02, and 0° represents 5rCeOs.
Represents oxygen that occupies the O position in eOs. ) Protons are generated due to such oxygen vacancies, and proton conductivity is said to occur. Possible proton generation mechanisms include processes [I] and (II) shown below.
（Ｉ ） Ｖ ａ ＋ Ｈｚ −一→２ Ｈ”〔発
明が解決しようとする問題点〕
現在、５ｒＣｅＯ，系プロトン導電性固体電解質で最も
導電率が高い組成は、５ｒＣｅａ、ａｓ Ｙｂｏ、ｏｓ
Ｏｓ−＊であるが、その導電率は、８５０℃において１
０−”Ｓ・ａｍ−’程度である。そしてこの値は、現在
広く利用されているイツトリア安定化ジルコニアの導電
率（１０−’Ｓ−値−１）に比べ、約ｌオーダ低い値で
ある。従って、今後プロトン導電体の広範な応用を図る
ためには、その導電率を向上させる必要がある。(I) V a + Hz −1 → 2 H” [Problem to be solved by the invention] Currently, the composition with the highest conductivity in the 5rCeO-based proton conductive solid electrolyte is 5rCea, as Ybo, os
Os-*, but its conductivity is 1 at 850°C.
This value is about 1 order of magnitude lower than the conductivity (10-'S-value-1) of yttria-stabilized zirconia, which is currently widely used. Therefore, in order to widen the application of proton conductors in the future, it is necessary to improve their conductivity.
本発明は、上記のような事情に鑑み、プロトン導電型固
体電解質の導電率を向上させることを目的として為され
たもので、その要旨は、ストロンチウムおよびセリウム
の酸化物を母体とし、さらにセリウムより酸素とのイオ
ン結合力が弱い金属元素の酸化物およびイツトリウム、
スカンジウム、インテルビウム、ネオジム、マグネシウ
ム、プラセオジムおよび亜鉛から選ばれた少なくとも１
種の金属元素の酸化物を含むことを特徴とするプロトン
導電性固体電解質にある。In view of the above-mentioned circumstances, the present invention was made for the purpose of improving the electrical conductivity of a proton conductive solid electrolyte. Oxides of metal elements with weak ionic bonding strength with oxygen and yttrium,
At least one selected from scandium, interbium, neodymium, magnesium, praseodymium and zinc
The present invention is a proton conductive solid electrolyte characterized by containing oxides of certain metal elements.
セリウムより酸素とのイオン結合力が弱い金属元素とし
ては例えばジルコニウム、チタン、錫などがある。Examples of metal elements having a weaker ionic bonding force with oxygen than cerium include zirconium, titanium, and tin.
上記のプロトン導電性固体電解質は下記一般式％式％
（ここで、ＭはＣｅより酸素とのイオン結合力が弱い金
属元素、例えばＺｒ 、Ｔ’ｉ 、Ｓｎを表わし、Ｍ
′はＹ、Ｓｃ 、Ｙｂ 、Ｎｄ 、Ｍｇ 、Ｐｒおよび
Ｚｎの少な（とも１種の金属元素を表わす、ｘ。The above proton conductive solid electrolyte is manufactured by the following general formula % (where M represents a metal element whose ionic bonding force with oxygen is weaker than that of Ce, such as Zr, T'i, Sn, and M
' is Y, Sc, Yb, Nd, Mg, Pr and Zn (both represent one type of metal element, x.
ｙはそれぞれＭ、Ｍ’のＣｅとの置換モル割合を表わし
、αはＭ、Ｍ’によるＣｅの置換によって規定される酸
素欠陥の割合を表わす、）この固体電解質において、Ｘ
の値は、Ｑ＜ｘ≦０．５の範囲、より好ましくはＱ＜ｘ
≦０．２の範囲をとる。また、ｙの値は、Ｑ＜ｙ≦０．
５の範囲、より好ましくはＱ＜ｙ≦０．１の範囲をとる
。In this solid electrolyte,
The value of is in the range of Q<x≦0.5, more preferably Q<x
The range is ≦0.2. Moreover, the value of y is Q<y≦0.
5, more preferably Q<y≦0.1.
本発明における固体酸化物中には該酸化物のプロトン導
電性を損なわない限りにおいて、Ｓｒ 。The solid oxide in the present invention may contain Sr as long as it does not impair the proton conductivity of the oxide.
Ｃｅ 、Ｍ （Ｚｎ 、Ｔｉ 、Ｓｎなど）、Ｍ
’（Ｙ、’Ｓｃ 、Ｙｂ 、Ｎｄ 、Ｍｇ 、 Ｐｒ
、 Ｚｎ）以外の金属等の不純物を含んでいてもよい
。５ｒＣｅＯ３などのペロプスカイト化合物は、ｙｂな
どのイオン添加によって、容易に欠陥構造をとる。以下
にその一例を示す。Ce, M (Zn, Ti, Sn, etc.), M
'(Y, 'Sc, Yb, Nd, Mg, Pr
, Zn) may also contain impurities such as metals other than Zn. A perovskite compound such as 5rCeO3 easily assumes a defective structure by adding ions such as yb. An example is shown below.
５ｒＣｅｏ、 ｑｓＹｂｏ、 ａｓ Ｏ＋−ｅｘそして
、プロトン導電性は、酸素欠陥の数に依存する。すなわ
ち、酸素欠陥数、αが大きな値であるほどプロトン導電
性は、大きくなる。5rCeo, qsYbo, as O+-ex and the proton conductivity depends on the number of oxygen vacancies. That is, the larger the number of oxygen vacancies, α, is, the greater the proton conductivity becomes.
一方、ペロブスカイトは、イオン性結晶である、従って
、イオン結晶性、すなわちイオン結合力を弱めれば、酸
素欠陥が生じ易くなると考えられる。On the other hand, perovskite is an ionic crystal, and therefore, if the ionic crystallinity, that is, the ionic bonding force is weakened, oxygen defects are likely to occur.
本発明者らは、Ｃｅの一部をＣｅより電気陰性度が大き
く酸素とのイオン結合力の弱い金属、例えばＺｎ、Ｔｉ
等で置換することによって、酸素イオンとの結合力が弱
まり、酸素欠陥が生じ易くなるため、プロトン導電性が
増大することを見い出した。The present inventors have proposed that a part of Ce be replaced with a metal that has higher electronegativity than Ce and weaker ionic bonding force with oxygen, such as Zn and Ti.
It has been found that by substituting with, for example, the bonding force with oxygen ions is weakened and oxygen vacancies are more likely to occur, thereby increasing proton conductivity.
イオン結晶性は、一般に、陽イオンと、陰イオンの電気
陰性度の差で示される。この場合、酸素との電気陰性度
の差が小さい陽イオンの方が、酸素イオンとのイオン結
合力が弱いことになる。表１に各陽イオンの電気陰性度
を示す。Ionic crystallinity is generally indicated by the difference in electronegativity between cations and anions. In this case, a cation with a smaller difference in electronegativity from oxygen has a weaker ionic bonding force with oxygen ions. Table 1 shows the electronegativity of each cation.
また、表２にＣｅ 、Ｚｒ 、Ｔｔ 、Ｈｆ 、
Ｓｎの各原子の０原子とのイオン結晶性を示す。Table 2 also shows Ce, Zr, Tt, Hf,
It shows the ionic crystallinity of each Sn atom with zero atoms.
表１、表２から、Ｚｒ、Ｔｉなどの場合、Ｃｅと比べて
イオン結晶性が低下することが認められる。From Tables 1 and 2, it is recognized that in the case of Zr, Ti, etc., the ionic crystallinity is lower than that of Ce.
このようにＣｅの一部をＣｅより０との結合力が弱い金
属元素、例えばＺｒで置換した場合、下記の如く酸素欠
陥数が大きくなることが推測され、実際、後出の実施例
で示されるように固体電解質の導電率が向上して、上記
の事情が確認された。In this way, when a part of Ce is replaced with a metal element whose bonding strength with 0 is weaker than that of Ce, for example, Zr, it is estimated that the number of oxygen vacancies increases as shown below, and in fact, as shown in the example below. The above situation was confirmed as the conductivity of the solid electrolyte improved.
すなわち、
５ｒＣｅ１１． ＊５Ｙｂｏ、 ｏｓｏｓ−ｅｘ Ｉ
＋５ｒＣｅｏ、＊ｓ−ｘ Ｚｒ、 Ｙｂｏ、ａｓ ｏ３
−＆ ｚにおいて、
α１くα２
であった。That is, 5rCe11. *5 Ybo, osos-ex I
+5rCeo, *s-x Zr, Ybo, as o3
- & z, α1 × α2.
本発明のプロトン導電性固体電解質の製造方法は特に限
定されず、従来知られている複合酸化物の製造方法のい
ずれによってもよい。代表的な方法では、目的とする金
属酸化物を構成する各金属の酸化物または焼成して酸化
物となる化合物（例、炭酸塩）の所定の割合の混合粉末
を仮焼した後、成形し、本焼して焼結体とする。The method for producing the proton conductive solid electrolyte of the present invention is not particularly limited, and any conventionally known method for producing complex oxides may be used. In a typical method, a mixed powder of a predetermined ratio of oxides of each metal constituting the desired metal oxide or a compound (e.g., carbonate) that becomes an oxide when fired is calcined, and then molded. , final firing to produce a sintered body.
第１図に、５ｒＣｅｏ、 ｑｓＹｂｏ、 ０５０３−
ａｔ ｒ （１）と５ｒＣｅｏ、 ７５ Ｚｒｏ、
ｚＹｂｏ、 ａｓ Ｏ：Ｉ−ｅｘ ｚ （２）および
、比較のために、（ＺｒＯｚ） ０．９ （ＹＪｓ）
ｏ、 ＋ （３）の導電率をそれぞれ示す。同図より、
〔２〕の電解質ではＺｒ添加によって８００℃以上の高
温で〔１〕の電解質よりプロトン導電性が増加し、８５
０℃では、はぼ酸素イオン導電体に匹適する導電率を示
すことが認められる。In Figure 1, 5rCeo, qsYbo, 0503-
at r (1) and 5rCeo, 75 Zro,
zYbo, as O:I-ex z (2) and, for comparison, (ZrOz) 0.9 (YJs)
The conductivities of o and + (3) are shown respectively. From the same figure,
In the electrolyte [2], the proton conductivity increases compared to the electrolyte [1] at high temperatures of 800°C or higher due to the addition of Zr, and the proton conductivity increases to 85
It is observed that at 0° C., the material exhibits a conductivity comparable to that of an oxygen ion conductor.
第２図に、５ｒＣｅ（１，９％−Ｘ ＺｒｙＹｂｏ、
ｏｓＯｘ−ｔｘ ｔにおいてＺｒの添加量Ｘを変えた時
の８５０℃での導電率の変化を示す。同図より、Ｚｒの
イオン半径がＣｅよりも小さいため、添加量が少ない場
合、イオンの導電通路が狭くなり一時導電率は減少する
が、Ｚｒ添加量の増大にともなって、酸素欠陥増加効果
が著しくなり、導電率は増大して行くことが認められる
。Figure 2 shows 5rCe (1,9%-X ZryYbo,
The graph shows the change in electrical conductivity at 850° C. when the amount of Zr added is changed in osOx-txt. From the same figure, since the ionic radius of Zr is smaller than that of Ce, when the amount added is small, the conductive path of the ions becomes narrow and the conductivity temporarily decreases, but as the amount of Zr added increases, the effect of increasing oxygen vacancies decreases. It is observed that the conductivity increases significantly.
下記に５ｒＣｅｏ、７ｓ Ｚｒｏ、ｚＹｏ、ｏｓ ０ｘ
−ｙの製造例を説明する。５ｒＣＯｉ粉末２２１．４５
ｇ 、 Ｃｅ０ｚ粉末１９３．６４ｇ 、 ＺｒＯ，粉
末３９．９７ ｇ 、 ＹｂｚＯｉ粉末１４．７８ ｇ
をそれぞれ秤量し、ポットミルで混合した後、これを１
３００℃に１０時間保持して仮焼粉末を得た。それから
、この仮焼粉末を成型後、１４００〜１５００℃の温度
で１２時間保持することによって焼結体を得た。Below are 5rCeo, 7s Zro, zYo, os 0x
An example of manufacturing -y will be explained. 5rCOi powder 221.45
g, Ce0z powder 193.64 g, ZrO, powder 39.97 g, YbzOi powder 14.78 g
Weigh each and mix in a pot mill, then add 1
A calcined powder was obtained by maintaining the temperature at 300°C for 10 hours. Then, this calcined powder was molded and held at a temperature of 1400 to 1500°C for 12 hours to obtain a sintered body.
本発明によれば、高温型プロトン導電性固体電解質の導
電率を酸素イオン導電体のそれに匹敵するまで高めるこ
とができ、プロトン導電性固体電解質の実用性を増大す
ることができる。According to the present invention, the conductivity of a high-temperature proton conductive solid electrolyte can be increased to be comparable to that of an oxygen ion conductor, and the practicality of the proton conductive solid electrolyte can be increased.
第１図は各種の固体電解質の導電率の温度変化を示すグ
ラフ図、第２図は本発明の実施例の固体電解質のＺｒ添
加量に関する導電率の変化を示すグラフ図である。
＄１図
（ｍ０１°／、）
Ｚｒ添加量
第２図FIG. 1 is a graph showing changes in electrical conductivity of various solid electrolytes with temperature, and FIG. 2 is a graph showing changes in electrical conductivity with respect to the amount of Zr added in solid electrolytes according to examples of the present invention. $1 figure (m01°/,) Zr addition figure 2
Claims (1)
、さらにセリウムより酸素とのイオン結合力が弱い金属
元素の酸化物と、 イットリウム、スカンジウム、イッテルビウム、ネオジ
ム、マグネシウム、プラセオジムおよび亜鉛から選ばれ
た少なくとも１種の金属元素の酸化物とを含むことを特
徴とするプロトン導電性固体電解質。 ２、セリウムより酸素とのイオン結合力が弱い前記金属
元素がジルコニウム、チタン、ハフニウム、ケイ素、ゲ
ルマニウム、鉛および錫から選ばれた少なくとも１種で
ある特許請求の範囲第１項記載のプロトン導電性固体電
解質。[Scope of Claims] 1. Based on oxides of strontium and cerium, and further comprising oxides of metal elements whose ionic bonding strength with oxygen is weaker than that of cerium, and yttrium, scandium, ytterbium, neodymium, magnesium, praseodymium, and zinc. A proton conductive solid electrolyte comprising an oxide of at least one selected metal element. 2. Proton conductivity according to claim 1, wherein the metal element having a weaker ionic bonding force with oxygen than cerium is at least one selected from zirconium, titanium, hafnium, silicon, germanium, lead, and tin. solid electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62028316A JPS63201051A (en) | 1987-02-12 | 1987-02-12 | Proton conductive solid electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62028316A JPS63201051A (en) | 1987-02-12 | 1987-02-12 | Proton conductive solid electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63201051A true JPS63201051A (en) | 1988-08-19 |
Family
ID=12245208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62028316A Pending JPS63201051A (en) | 1987-02-12 | 1987-02-12 | Proton conductive solid electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63201051A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19535922A1 (en) * | 1995-09-27 | 1997-04-10 | Forschungszentrum Juelich Gmbh | New strontium-cerium-zirconium oxide ceramic |
| JP2003033662A (en) * | 2001-07-23 | 2003-02-04 | Sumitomo Metal Mining Co Ltd | Photocatalyst exhibiting catalytic activity in visible light region |
| JP2008243627A (en) * | 2007-03-27 | 2008-10-09 | Toyota Motor Corp | Proton conductor, electrochemical cell, and manufacturing method of proton conductor |
-
1987
- 1987-02-12 JP JP62028316A patent/JPS63201051A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19535922A1 (en) * | 1995-09-27 | 1997-04-10 | Forschungszentrum Juelich Gmbh | New strontium-cerium-zirconium oxide ceramic |
| JP2003033662A (en) * | 2001-07-23 | 2003-02-04 | Sumitomo Metal Mining Co Ltd | Photocatalyst exhibiting catalytic activity in visible light region |
| JP4696414B2 (en) * | 2001-07-23 | 2011-06-08 | 住友金属鉱山株式会社 | Photocatalyst having catalytic activity in the visible light region |
| JP2008243627A (en) * | 2007-03-27 | 2008-10-09 | Toyota Motor Corp | Proton conductor, electrochemical cell, and manufacturing method of proton conductor |
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