JP2810104B2 - Ceramic electrode and fuel cell having the same - Google Patents
Ceramic electrode and fuel cell having the sameInfo
- Publication number
- JP2810104B2 JP2810104B2 JP1110815A JP11081589A JP2810104B2 JP 2810104 B2 JP2810104 B2 JP 2810104B2 JP 1110815 A JP1110815 A JP 1110815A JP 11081589 A JP11081589 A JP 11081589A JP 2810104 B2 JP2810104 B2 JP 2810104B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- fuel cell
- ceramic
- weight
- ceramic material
- 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.)
- Expired - Lifetime
Links
- 239000000446 fuel Substances 0.000 title claims description 23
- 239000000919 ceramic Substances 0.000 title claims description 18
- 229910010293 ceramic material Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 150000002739 metals Chemical class 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 description 11
- 239000011572 manganese Substances 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- -1 organic acid salt Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910003367 La0.5Sr0.5MnO3 Inorganic materials 0.000 description 1
- 229910002182 La0.7Sr0.3MnO3 Inorganic materials 0.000 description 1
- 229910017771 LaFeO Inorganic materials 0.000 description 1
- 241000877463 Lanio Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Fuel Cell (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inert Electrodes (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はセラミックス電極及びこれを有する燃料電池
に関するものである。Description: TECHNICAL FIELD The present invention relates to a ceramic electrode and a fuel cell having the same.
（従来の技術） 最近、燃料電池、特に固体電解質型燃料電池が、発電
装置として注目されている。これは、発電効率が高く、
燃料の多様化が可能で（ナフサ，天然ガス，メタノー
ル，石炭改質ガス、重油等）、低公害で、しかも発電効
率が設備規模によって影響されず、極めて有望な技術で
ある。(Prior Art) Recently, fuel cells, particularly solid oxide fuel cells, have been receiving attention as power generation devices. This is high power generation efficiency,
It is a promising technology that can diversify fuels (naphtha, natural gas, methanol, coal reformed gas, heavy oil, etc.), has low pollution, and its power generation efficiency is not affected by equipment scale.
ことに、固体電解質型燃料電池は、エネルギー変換効
率が著しく高い、等の長所を有している。In particular, the solid oxide fuel cell has such advantages that the energy conversion efficiency is extremely high.
固体電解質型燃料電池の空気電極（カソード）は、10
00℃の酸素の存在する雰囲気中で動作しなければなら
ず、酸化性雰囲気で安定なことが必要なので、通常の金
属は使用できない。また、貴金属もコストの面から実用
に適さない。このために、多くの酸化物が空気電極材と
して試作、検討されている。The air electrode (cathode) of a solid oxide fuel cell is 10
Since it must operate in an atmosphere where oxygen is present at 00 ° C. and must be stable in an oxidizing atmosphere, ordinary metals cannot be used. Also, noble metals are not suitable for practical use in terms of cost. For this reason, many oxides have been experimentally manufactured and studied as air electrode materials.
空気電極の役割は、電解質へ電子と酸素を供給し、O2
分子をイオン解離することである。このために、開孔性
気孔に富んでおり、かつ電子導電性が大きく、イオン解
離触媒作用が高くなければならない。また、化学的安定
性の高いこと、固体電解質との接着性・熱膨張の整合が
とれていることも必要である。こうした空気電極材とし
て確定的なものは未だなく、良好な電極材料の出現が待
望されている。The role of air electrode supplies the electrons and oxygen to the electrolyte, O 2
Ion dissociation of molecules. For this purpose, it must be rich in open pores, have high electron conductivity, and have high ion dissociation catalytic action. In addition, it is necessary that chemical stability is high and that adhesion and thermal expansion with the solid electrolyte are matched. There is no definitive air electrode material yet, and the emergence of a good electrode material is expected.
最近、電子導電性のみならず、イオン導電性もあわせ
有する混合導電性酸化物の研究が進み、ランタニド元素
を用いた複合酸化物が使われるようになっている（特開
昭57−113561号）。特に、ペロブスカイト構造の複合酸
化物であるLaCoO3,La1-xSrxMnO3（特開昭63−261678号
等）、LaNiO3,LaFeO3等の空気電極への適用が検討され
ている。Recently, research on mixed conductive oxides having not only electronic conductivity but also ionic conductivity has been advanced, and composite oxides using lanthanide elements have been used (Japanese Patent Laid-Open No. 57-113561). . In particular, application to air electrodes such as LaCoO 3 , La 1-x Sr x MnO 3 (Japanese Unexamined Patent Publication No. 63-261678) and LaNiO 3 , LaFeO 3 which are composite oxides having a perovskite structure is being studied.
（発明が解決しようとする課題） しかし、従来技術では、空気電極の機械的強度が低
く、電池製造プロセス中に破損したり、電池の耐久性が
低いという問題があった。従って、構造材料として、よ
り高強度の空気電極を形成する技術が要請されている。(Problems to be Solved by the Invention) However, in the related art, there were problems that the mechanical strength of the air electrode was low, and the air electrode was damaged during the battery manufacturing process, and the durability of the battery was low. Therefore, there is a demand for a technique for forming a higher strength air electrode as a structural material.
本発明の課題は、強度が高く、電気的特性、化学的安
定性が高く、固体電解質等との熱膨張の整合を実現で
き、運転中の耐久性に優れ、電池製造プロセス中の破損
を防止できるようなセラミックス電極及びこれを用いた
燃料電池を提供することである。It is an object of the present invention to have high strength, high electrical characteristics and high chemical stability, to achieve matching of thermal expansion with a solid electrolyte, etc., to have excellent durability during operation, and to prevent damage during the battery manufacturing process. An object of the present invention is to provide a ceramic electrode and a fuel cell using the same.
（課題を解決するための手段） 本発明は、組成物La1-xSrxMnO3〔ただし、０＜ｘ≦0.
5〕100重量部に対し、Si,Ti,Fe,Al,B,Cu,Co,Mnからなる
群より選ばれた一種以上の金属の酸化物を合計量で2.0
重量部以下含有させたセラミックス素材からなるセラミ
ックス電極に係るものである。(Means for Solving the Problems) The present invention relates to a composition La 1-x Sr x MnO 3 [where 0 <x ≦ 0.
5) For 100 parts by weight, oxides of one or more metals selected from the group consisting of Si, Ti, Fe, Al, B, Cu, Co, Mn in a total amount of 2.0
The present invention relates to a ceramic electrode made of a ceramic material containing not more than parts by weight.
また、本発明は、前記セラミックス素材からなるセラ
ミックス電極を、空気電極として有する燃料電池に係る
ものである。Further, the present invention relates to a fuel cell having a ceramic electrode made of the ceramic material as an air electrode.
また、本発明は、下記〔Ｉ〕のセラミックス素材又は
下記〔II〕のセラミックス素材により形成されたセラミ
ックス電極に係るものである。The present invention also relates to a ceramic electrode formed from the following ceramic material [I] or the following ceramic material [II].
〔Ｉ〕La1-xSrxMn1-yAyO3〔ただし、ＡはCu,Zn,Fe,Co,A
l,Ti,Mgからなる群より選ばれた一種以上の金属で、 ０＜ｘ≦0.5。[I] La 1-x Sr x Mn 1-y A y O 3 [where A is Cu, Zn, Fe, Co, A
One or more metals selected from the group consisting of l, Ti, and Mg, where 0 <x ≦ 0.5.
０＜ｙ≦0.3。〕 の組成を有するセラミックス素材。0 <y ≦ 0.3. ] The ceramic material which has the composition of.
〔II〕組成物La1-xSrxMn1-yAyO3〔ただし、ＡはCu,Zn,N
i,Fe,Co,Cr,Al,Ti,Mgからなる群より選ばれた一種以上
の金属で、 ０＜ｘ≦0.5。[II] Composition La 1-x Sr x Mn 1-y A y O 3 [where A is Cu, Zn, N
One or more metals selected from the group consisting of i, Fe, Co, Cr, Al, Ti, and Mg, where 0 <x ≦ 0.5.
０＜ｙ≦0.3。〕 100重量部に対し、Si,Ti,Fe,Al,B,Cu,Co,Mnからなる群
より選ばれた一種以上の金属の酸化物を合計量で2.0重
量部以下含有させたセラミックス素材。0 <y ≦ 0.3. ] A ceramic material containing 100 parts by weight of oxides of one or more metals selected from the group consisting of Si, Ti, Fe, Al, B, Cu, Co, and Mn in a total amount of 2.0 parts by weight or less.
また、本発明は、前記〔Ｉ〕のセラミックス素材又は
前記〔II〕のセラミックス素材により形成されたセラミ
ックス電極を、空気電極として有する燃料電池に係るも
のである。Further, the present invention relates to a fuel cell having, as an air electrode, a ceramic electrode formed of the ceramic material [I] or the ceramic material [II].
なお、上記において、「金属の酸化物」としては、S
i,Ti,Feの酸化物が特に好ましい。In the above, the “metal oxide” is S
Oxides of i, Ti and Fe are particularly preferred.
金属の酸化物の含有量は，上記において、更に0.1〜
1.0重量部とすることが好ましい。The content of the metal oxide is 0.1 to
Preferably it is 1.0 part by weight.
ｘの範囲としては、更に0.1≦ｘ≦0.3が好ましい。 The range of x is more preferably 0.1 ≦ x ≦ 0.3.
Ａとしては、Cu,Znが特に好ましい。 As A, Cu and Zn are particularly preferred.
ｙの範囲としては、更に0.05≦ｙ≦0.2が好ましい。 The range of y is more preferably 0.05 ≦ y ≦ 0.2.
（作 用） 本発明者は、La1-xSrxMnO3100重量部に対し、上記の
金属酸化物を2.0重量部以下の特定の割合で添加する
と、セラミックス電極強度が著しく向上することを見出
した。しかも、驚くべきことに、この添加量では、電気
伝導度が低下せず、かつ熱膨張係数にも影響しなかった
のである。また、上記のようにｘ≦0.5とすると、熱膨
張係数がZrO2（固体電解質）の熱膨張係数と近似し、電
極差上適合する。仮に、金属酸化物の添加量が2.0重量
部を超えると、電気伝導度が著しく低下し、強度もかえ
って低下する。(Operation) The present inventors have found that adding the above metal oxide in a specific ratio of 2.0 parts by weight or less to 100 parts by weight of La 1-x Sr x MnO 3 significantly improves the strength of the ceramic electrode. I found it. Moreover, surprisingly, this addition amount did not decrease the electric conductivity and did not affect the coefficient of thermal expansion. Further, when x ≦ 0.5 as described above, the coefficient of thermal expansion approximates the coefficient of thermal expansion of ZrO 2 (solid electrolyte), and is suitable for the electrode difference. If the addition amount of the metal oxide exceeds 2.0 parts by weight, the electric conductivity is remarkably reduced, and the strength is rather lowered.
また、上記〔Ｉ〕のセラミックス素材では、マンガン
の一部を特定の金属で置換している。そして、A,x,yを
前記のように特定することで、このセラミックス素材か
らなる電極の強度が上記と同様に著しく向上し、しかも
電気伝導度，熱膨張係数の整合性を損なわなかったので
ある。また、上記〔II〕のセラミックス素材により電極
を形成したときにも同様の作用があった。In the ceramic material [I], a part of manganese is replaced by a specific metal. By specifying A, x, and y as described above, the strength of the electrode made of the ceramic material was remarkably improved in the same manner as described above, and the electrical conductivity and the coefficient of thermal expansion were not impaired. is there. The same effect was obtained when the electrodes were formed from the ceramic material of [II].
仮に、ｘ＞0.5とすると、熱膨張係数がZrO2のそれか
ら大きく外れてくる。また、ｙ＞0.3では組成物のMn位
置へのドーピングは困難である。If x> 0.5, the thermal expansion coefficient greatly deviates from that of ZrO 2 . When y> 0.3, doping of the composition at the Mn position is difficult.
なお、高強度化の原因のひとつは、材料の焼結性が良
くなり、気孔率が低下することであるが、それ以外にも
材料的及び微構造的な変化が強度向上に寄与していると
思われる。One of the causes of the increase in strength is that the sinterability of the material is improved and the porosity is reduced, but other changes in the material and microstructure contribute to the improvement in strength. I think that the.
これらの特定の高強度セラミックス電極を、燃料電池
の空気電極として採用することで、空気電極の強度ひい
ては燃料電池構造体全体の強度が増し、電気特性の良い
ものとなる。また、電池製造プロセスにおいて破損が減
少し、燃料電池の耐久性及び性能が向上する。By employing these specific high-strength ceramic electrodes as the air electrode of the fuel cell, the strength of the air electrode and thus the strength of the entire fuel cell structure are increased, and the electrical characteristics are improved. Further, damage in the cell manufacturing process is reduced, and the durability and performance of the fuel cell are improved.
（実施例） 最初に燃料電池について説明する。(Example) First, a fuel cell will be described.
燃料電池は、燃料が有する化学エネルギーを直接電気
エネルギーに変換できる装置で、カルノーサイクルの制
約を受けないため、本質的に高いエネルギー変換効率を
有し、環境保全性も良好であるなどの特徴を持ってい
る。A fuel cell is a device that can directly convert the chemical energy of fuel into electric energy, and is not subject to the limitations of the Carnot cycle.It has inherently high energy conversion efficiency and good environmental preservation. have.
また、固体電解質型燃料電池（SOFC）は、1000℃の高
温で作動するため電極反応が極めて活発で、高価な白金
などの貴金属触媒を全く必要とせず、分極が小さく、出
力電圧も比較的高いため、エネルギー変換効率が他の燃
料電池にくらべ著しく高い。更に、構造材は全て固体か
ら構成されるため、安定且つ長寿命である。The solid oxide fuel cell (SOFC) operates at a high temperature of 1000 ° C, so the electrode reaction is extremely active, does not require expensive noble metal catalysts such as platinum, has small polarization, and has a relatively high output voltage. Therefore, the energy conversion efficiency is significantly higher than other fuel cells. Further, since all the structural materials are composed of solids, they have a stable and long life.
SOFC単電池の構成要素は、一般的に空気電極、固体電
解質、燃料電極からなり、また、単電池の直列接続に、
インターコネクターを使用する。The components of a SOFC cell generally consist of an air electrode, a solid electrolyte, and a fuel electrode.
Use interconnectors.
本実施例は、このSOFCの空気電極として最適なセラミ
ックス電極、及びこれを空気電極として有する固体電解
質型燃料電池に関わるものである。The present embodiment relates to a ceramic electrode which is optimal as an air electrode of this SOFC, and a solid oxide fuel cell having this as an air electrode.
SOFCの空気電極として本発明に関わるセラミックス電
極を使用すれば、空気電極の強度が増し、SOFC製造時及
び発電動作時の剥離、欠陥、破損が少なくなって、極め
て有利である。If the ceramic electrode according to the present invention is used as the air electrode of the SOFC, the strength of the air electrode is increased, and peeling, defects, and breakage during SOFC production and power generation operation are reduced, which is extremely advantageous.
次に、空気電極の構造例及び強度評価等について述べ
る。Next, an example of the structure of the air electrode and evaluation of the strength will be described.
実施例１ 純度99.9％のLa2O3106.1gと、純度96％のMnO268.4g
と、純度99.1％のSrCO310.8gとを秤量した。玉石800g
と、水200gと、前記秤量した３種の化合物を、２のボ
ールミルに入れ、３時間混合してスラリーとした。この
スラリーを110℃で20時間乾燥した後、乾燥物を149μｍ
以下に解砕し、空気中1200℃で10時間仮焼し、La0.9Sr
0.1MnO3を合成した。La0.95Sr0.05MnO3,La0.8Sr0.2Mn
O3,La0.7Sr0.3MnO3,La0.5Sr0.5MnO3,La0.4Sr0.6MnO3な
ども、その組成に調合し、前記La0.9Sr0.1MnO3同様な手
法で合成した。また、これら組成物を合成する際の出発
原料は、酸化物に限らず、炭酸塩、硝酸塩、酢酸塩、硫
酸塩、水酸化物などでも良い。さらに合成法としては、
ここに示した固相反応法に限らず、溶液からの共沈法や
有機酸塩の熱分解でもよい。このように得られた組成物
100重量部に対し、純度99.9％のSiO2,TiO2,Fe2O3,Al
2O3,B2O3,CuO,CoO,MnO2を0.1〜3.0重量部添加し、混合
物を得た。この混合物に100重量部（外配）加えてボー
ルミルで20時間混合粉砕し、乾燥後、解砕して、粉末と
した。次いで、この粉末を圧力200kgf/cm2で金型プレス
成形し、さらに圧力2.5t/cm2でラバープレスし、60mm×
60mm×8mmの成形体を得た。これを空気中1450℃で10時
間焼成し、表１に示す電極材料を得た。Example 1 106.1 g of La 2 O 3 having a purity of 99.9% and 68.4 g of MnO 2 having a purity of 96%
And 10.8 g of SrCO 3 having a purity of 99.1% were weighed. 800g cobblestone
, 200 g of water, and the weighed three compounds were put into a 2 ball mill and mixed for 3 hours to form a slurry. After drying this slurry at 110 ° C. for 20 hours, the dried product was 149 μm
Crushed below, calcined in air at 1200 ° C for 10 hours, La 0.9 Sr
0.1 MnO 3 was synthesized. La 0.95 Sr 0.05 MnO 3 , La 0.8 Sr 0.2 Mn
O 3 , La 0.7 Sr 0.3 MnO 3 , La 0.5 Sr 0.5 MnO 3 , La 0.4 Sr 0.6 MnO 3, etc. were also prepared according to the composition and synthesized by the same method as in the above-mentioned La 0.9 Sr 0.1 MnO 3 . The starting materials for synthesizing these compositions are not limited to oxides, but may be carbonates, nitrates, acetates, sulfates, hydroxides, and the like. Furthermore, as a synthesis method,
The method is not limited to the solid-phase reaction method shown here, but may be a coprecipitation method from a solution or thermal decomposition of an organic acid salt. The composition thus obtained
99.9% pure SiO 2 , TiO 2 , Fe 2 O 3 , Al
0.1 to 3.0 parts by weight of 2 O 3 , B 2 O 3 , CuO, CoO, and MnO 2 were added to obtain a mixture. 100 parts by weight (external) was added to this mixture, mixed and pulverized for 20 hours with a ball mill, dried, and crushed to obtain a powder. Next, this powder was press-molded at a pressure of 200 kgf / cm 2 and further rubber-pressed at a pressure of 2.5 t / cm 2 to obtain a 60 mm ×
A molded body of 60 mm × 8 mm was obtained. This was fired in air at 1450 ° C. for 10 hours to obtain an electrode material shown in Table 1.
各電極材料につき、以下に示す特性試験を行った。結
果を表１に示す。The following characteristic tests were performed for each electrode material. Table 1 shows the results.
四点曲げ強度:JIS R−1601「ファインセラミックスの
曲げ強さ試験方法」の四点曲げ強度で測定した。試料形
状は３×４×10mm,外側スパンは30mm,内側スパンは10mm
で行った。Four-point bending strength: Measured by four-point bending strength according to JIS R-1601 “Testing method for bending strength of fine ceramics”. Sample shape is 3 × 4 × 10mm, outer span is 30mm, inner span is 10mm
I went in.
熱膨張係数測定：（株）リガクのTMA−2S型熱膨張計
を用い、試料形状φ５×50mmで40〜900℃の範囲で測定
した。Thermal expansion coefficient measurement: Using a TMA-2S thermal dilatometer of Rigaku Co., Ltd., the sample was measured at a sample shape of φ5 × 50 mm in the range of 40 to 900 ° C.
電気伝導度：φ30×6mmの試料に白金線を間隔5mmで４
本取付け、温度1000℃空気中にて、直流四端子法で測定
した。Electric conductivity: 4 pieces of platinum wire at 5mm interval on a sample of φ30 × 6mm
The measurement was performed by the DC four-terminal method in the air with the temperature of 1000 ° C and the actual mounting.
気孔率：開気孔率を水置換法で測定した。 Porosity: The open porosity was measured by a water displacement method.
実施例２ 純度99.9％のLa2O3106.1gと、純度96％のMnO259.2g
と、純度99.1％のSrCO310.8gと、純度99.5％のCuO5.8g
を秤量した。玉石800gと、水200gと、前記秤量した４種
の化合物を、２のボールミルに入れ、３時間混合して
スラリーとした。このスラリーを110℃で20時間乾燥し
た後、乾燥物を149μｍ以下に解砕し、空気中1200℃で1
0時間仮焼し、La0.9Sr0.1Mn0.9Cu0.1O3を合成した。La
0.9Sr0.1Mn0.8Cu0.2O3、La0.9Sr0.1Mn0.7Cu0.3O3なども
その組成に調合し、La0.9Sr0.1Mn0.9Cu0.1O3と同様な手
法で合成した。またCuOの代わりにZnO,NiO,Fe2O3,TiO2,
Al2O3,CoO,Cr2O3,MgOを用いて調合し、表２に挙げた組
成物を合成した。また、実施例１と同様に、合成する際
の出発原料は、酸化物に限らず、炭酸塩、硝酸塩、酢酸
塩、硫酸塩、水酸化物などでも良い。さらに、合成法と
しては、ここに示した固相反応法に限らず、溶液からの
共沈法や有機酸塩の熱分解も可能である。このように得
られた組成物100重量部に対し、純度99.9％のSiO2,Ti
O2,Fe2O3をそれぞれ表２に示す量添加し、混合物を得
た。この混合物に水分100重量部（外配）加えてボール
ミルで20時間混合粉砕し、乾燥後、解砕して、粉末とし
た。次いで、この粉末を圧力20kgf/cm2で金型プレス成
形し、さらに圧力2.5t/cm2でラバープレスし、60mm×60
mm×8mmの成形体を得た。これを空気中1450℃で10時間
焼成し、表２に示す電極材料を得た。 Example 2 106.1 g of La 2 O 3 having a purity of 99.9% and 59.2 g of MnO 2 having a purity of 96%
And 99.1% pure SrCO 3 10.8g and 99.5% pure CuO5.8g
Was weighed. 800 g of boulders, 200 g of water, and the four weighed compounds were placed in a 2 ball mill and mixed for 3 hours to form a slurry. After drying this slurry at 110 ° C. for 20 hours, the dried product was crushed to 149 μm or less, and dried in air at 1200 ° C. for 1 hour.
By calcining for 0 hour, La 0.9 Sr 0.1 Mn 0.9 Cu 0.1 O 3 was synthesized. La
0.9 Sr 0.1 Mn 0.8 Cu 0.2 O 3 , La 0.9 Sr 0.1 Mn 0.7 Cu 0.3 O 3, etc. were also prepared according to the composition, and synthesized by the same method as La 0.9 Sr 0.1 Mn 0.9 Cu 0.1 O 3 . Also, instead of CuO, ZnO, NiO, Fe 2 O 3 , TiO 2 ,
The compositions listed in Table 2 were synthesized using Al 2 O 3 , CoO, Cr 2 O 3 , and MgO. Further, as in the first embodiment, the starting materials for the synthesis are not limited to oxides, but may be carbonates, nitrates, acetates, sulfates, hydroxides, and the like. Further, the synthesis method is not limited to the solid-phase reaction method described here, but may be a coprecipitation method from a solution or thermal decomposition of an organic acid salt. With respect to 100 parts by weight of the composition thus obtained, 99.9% pure SiO 2 , Ti
O 2 and Fe 2 O 3 were added in the amounts shown in Table 2 to obtain mixtures. To this mixture was added 100 parts by weight of water (external part), mixed and pulverized with a ball mill for 20 hours, dried, and crushed to obtain a powder. Next, this powder was press-molded at a pressure of 20 kgf / cm 2 and further rubber-pressed at a pressure of 2.5 t / cm 2 to obtain a 60 mm × 60
A compact of mm × 8 mm was obtained. This was fired in air at 1450 ° C. for 10 hours to obtain an electrode material shown in Table 2.
各電極材料につき、実施例１と同じ測定法により、特
性試験を行った。結果を表２に示す。For each electrode material, a characteristic test was performed by the same measurement method as in Example 1. Table 2 shows the results.
表１、表２に示したように本発明の実施例は、いずれ
も特許請求範囲に限定した添加量及び置換量の範囲内で
のみ強度が比較例より著しく高い。且つ電気伝導度も高
く置換や添加をしない場合と比較しても低下は殆ど見ら
れない。また、熱膨張係数は、僅かながら低下するもの
もあるが、強度向上が大きいことを考えればこの低下は
許容範囲である。むしろ固体電解質型燃料電池の空気電
極への適用を考えた場合、熱膨張係数は固体電解質のそ
れ（8mol％Y2O3−ZrO2で10×106K-1）に整合させる必要
があり、好都合と言える。 As shown in Tables 1 and 2, the examples of the present invention have remarkably higher strengths than those of the comparative examples only within the range of the addition amount and the substitution amount defined in the claims. In addition, the electric conductivity is high and almost no decrease is observed as compared with the case where substitution or addition is not performed. In addition, the thermal expansion coefficient is slightly reduced in some cases, but considering that the strength improvement is large, this reduction is within an allowable range. Rather, considering the application to the air electrode of a solid oxide fuel cell, the coefficient of thermal expansion must be matched to that of the solid electrolyte (10 × 10 6 K -1 with 8 mol% Y 2 O 3 -ZrO 2 ). It is convenient.
なお、実施例1,2における製造法のフローチャートを
第１図に示す。また、実施例中の本発明の代表的な３試
料と比較例との特性の比較を第２図に記載する。FIG. 1 shows a flowchart of the manufacturing method in Examples 1 and 2. FIG. 2 shows a comparison of characteristics between three representative examples of the present invention in Examples and Comparative Examples.
本発明に係るセラミックス電極は、円筒状SOFC、自己
支持型の円筒型SOFC、平板型SOFC、一体型SOFC等にも適
用できる。The ceramic electrode according to the present invention can be applied to a cylindrical SOFC, a self-supporting cylindrical SOFC, a flat-plate SOFC, an integrated SOFC, and the like.
また、SOFCの各部の寸法、形状、構造、各SOFC単位セ
ルの接続方法、配列の個数、配列方法等は種々変更でき
る。In addition, the dimensions, shape, and structure of each part of the SOFC, the connection method of each SOFC unit cell, the number of arrangements, the arrangement method, and the like can be variously changed.
【図面の簡単な説明】 第１図は本発明に係るセラミックス電極の製造例を示す
フローチャート、 第２図は実施例、比較例の各試料の特性を示すグラフで
ある。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart showing a production example of a ceramic electrode according to the present invention, and FIG. 2 is a graph showing characteristics of each sample of an example and a comparative example.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 4/86 - 4/98──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. 6 , DB name) H01M 4/86-4/98
Claims (4)
5〕100重量部に対し、Si,Ti,Fe,Al,B,Cu,Co,Mnからなる
群より選ばれた一種以上の金属の酸化物を合計量で2.0
重量部以下含有させたセラミックス素材からなるセラミ
ックス電極。The composition La 1-x Sr x MnO 3 [where 0 <x ≦ 0.
5) For 100 parts by weight, oxides of one or more metals selected from the group consisting of Si, Ti, Fe, Al, B, Cu, Co, Mn in a total amount of 2.0
A ceramic electrode made of a ceramic material containing not more than parts by weight.
〔II〕のセラミックス素材により形成されたセラミック
ス電極。 〔Ｉ〕La1-xSrxMn1-yAyO3〔ただし、ＡはCu,Zn,Fe,Co,A
l,Ti,Mgからなる群より選ばれた一種以上の金属で、 ０＜ｘ≦0.5。 ０＜ｙ≦0.3。〕 の組成を有するセラミックス素材。 〔II〕組成物La1-xSrxMn1-yAyO3〔ただし、ＡはCu,Zn,N
i,Fe,Co,Cr,Al,Ti,Mgからなる群より選ばれた一種以上
の金属で、 ０＜ｘ≦0.5。 ０＜ｙ≦0.3。〕 100重量部に対し、Si,Ti,Fe,Al,B,Cu,Co,Mnからなる群
より選ばれた一種以上の金属の酸化物を合計量で2.0重
量部以下含有させたセラミックス素材。2. A ceramic electrode formed of a ceramic material of the following [I] or a ceramic material of the following [II]. [I] La 1-x Sr x Mn 1-y A y O 3 [where A is Cu, Zn, Fe, Co, A
One or more metals selected from the group consisting of l, Ti, and Mg, where 0 <x ≦ 0.5. 0 <y ≦ 0.3. ] The ceramic material which has the composition of. [II] Composition La 1-x Sr x Mn 1-y A y O 3 [where A is Cu, Zn, N
One or more metals selected from the group consisting of i, Fe, Co, Cr, Al, Ti, and Mg, where 0 <x ≦ 0.5. 0 <y ≦ 0.3. ] A ceramic material containing 100 parts by weight of oxides of one or more metals selected from the group consisting of Si, Ti, Fe, Al, B, Cu, Co, and Mn in a total amount of 2.0 parts by weight or less.
5〕100重量部に対し、Si,Ti,Fe,Al,B,Cu,Co,Mnからなる
群より選ばれた一種以上の金属の酸化物を合計量で2.0
重量部以下含有させたセラミックス素材からなるセラミ
ックス電極を、空気電極として有する燃料電池。3. Composition La 1-x Sr x MnO 3 [where 0 <x ≦ 0.
5) For 100 parts by weight, oxides of one or more metals selected from the group consisting of Si, Ti, Fe, Al, B, Cu, Co, Mn in a total amount of 2.0
A fuel cell comprising, as an air electrode, a ceramic electrode made of a ceramic material containing not more than parts by weight.
〔II〕のセラミックス素材により形成されたセラミック
ス電極を、空気電極として有する燃料電池。 〔Ｉ〕La1-xSrxMn1-yAyO3〔ただし、ＡはCu,Zn,Fe,Co,A
l,Ti,Mgからなる群より選ばれた一種以上の金属で、 ０＜ｘ≦0.5。 ０＜ｙ≦0.3。〕 の組成を有するセラミックス素材。 〔II〕組成物La1-xSrxMn1-yAyO3〔ただし、ＡはCu,Zn,N
i,Fe,Co,Cr,Al,Ti,Mgからなる群より選ばれた一種以上
の金属で、 ０＜ｘ≦0.5。 ０＜ｙ≦0.3。〕 100重量部に対し、Si,Ti,Fe,Al,B,Cu,Co,Mnからなる群
より選ばれた一種以上の金属の酸化物を合計量で2.0重
量部以下含有させたセラミックス素材。4. A fuel cell comprising, as an air electrode, a ceramic electrode formed of a ceramic material of the following [I] or a ceramic material of the following [II]. [I] La 1-x Sr x Mn 1-y A y O 3 [where A is Cu, Zn, Fe, Co, A
One or more metals selected from the group consisting of l, Ti, and Mg, where 0 <x ≦ 0.5. 0 <y ≦ 0.3. ] The ceramic material which has the composition of. [II] Composition La 1-x Sr x Mn 1-y A y O 3 [where A is Cu, Zn, N
One or more metals selected from the group consisting of i, Fe, Co, Cr, Al, Ti, and Mg, where 0 <x ≦ 0.5. 0 <y ≦ 0.3. ] A ceramic material containing 100 parts by weight of oxides of one or more metals selected from the group consisting of Si, Ti, Fe, Al, B, Cu, Co, and Mn in a total amount of 2.0 parts by weight or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1110815A JP2810104B2 (en) | 1989-04-28 | 1989-04-28 | Ceramic electrode and fuel cell having the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1110815A JP2810104B2 (en) | 1989-04-28 | 1989-04-28 | Ceramic electrode and fuel cell having the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02288159A JPH02288159A (en) | 1990-11-28 |
| JP2810104B2 true JP2810104B2 (en) | 1998-10-15 |
Family
ID=14545363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1110815A Expired - Lifetime JP2810104B2 (en) | 1989-04-28 | 1989-04-28 | Ceramic electrode and fuel cell having the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2810104B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5432024A (en) * | 1992-10-14 | 1995-07-11 | Ngk Insulators, Ltd. | Porous lanthanum manganite sintered bodies and solid oxide fuel cells |
| DE4237602A1 (en) * | 1992-11-06 | 1994-05-11 | Siemens Ag | High temperature fuel cell stack and process for its manufacture |
| EP0902493B1 (en) * | 1997-09-11 | 2001-01-03 | Sulzer Hexis AG | Elektrochemical active element for a solid oxide fuel cell |
| EP1081778A4 (en) | 1998-04-21 | 2006-03-01 | Toto Ltd | Solid electrolyte fuel cell and method of producing the same |
| GB0217794D0 (en) * | 2002-08-01 | 2002-09-11 | Univ St Andrews | Fuel cell electrodes |
| JP4720238B2 (en) * | 2004-12-09 | 2011-07-13 | 日産自動車株式会社 | Air electrode for solid oxide fuel cell and method for producing the same |
| JP5272572B2 (en) * | 2008-05-21 | 2013-08-28 | 株式会社村田製作所 | Interconnector material, cell separation structure, and solid oxide fuel cell |
| JP5574881B2 (en) * | 2010-08-19 | 2014-08-20 | Ａｇｃセイミケミカル株式会社 | Air electrode material powder for solid oxide fuel cell and method for producing the same |
| JP5543297B2 (en) * | 2010-08-25 | 2014-07-09 | Ａｇｃセイミケミカル株式会社 | Air electrode material powder for solid oxide fuel cell and method for producing the same |
| CN108714426B (en) * | 2018-06-15 | 2021-06-08 | 武汉理工大学 | Nano cubic perovskite type catalyst and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6358765A (en) * | 1986-08-29 | 1988-03-14 | Toa Nenryo Kogyo Kk | Oxygen electrode structure for high temperature solid electrolyte fuel cell |
| JP2511095B2 (en) * | 1988-02-05 | 1996-06-26 | 三菱重工業株式会社 | Electrode material |
-
1989
- 1989-04-28 JP JP1110815A patent/JP2810104B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02288159A (en) | 1990-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7838141B2 (en) | Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices | |
| JP2790653B2 (en) | Conductive intermediate connector and fuel cell having the same | |
| JPH04341765A (en) | Manufacture of lanthanum chromite film and interconnector for solid electrolyte fuel cell | |
| JP2810104B2 (en) | Ceramic electrode and fuel cell having the same | |
| KR101549443B1 (en) | Method for manufacturing symmetrical solid oxide fuel cell having double perovskite structure | |
| US20040214070A1 (en) | Low sintering lanthanum ferrite materials for use as solid oxide fuel cell cathodes and oxygen reduction electrodes and other electrochemical devices | |
| KR20130075529A (en) | Solid oxide electrode, solid oxide fuel cell containing solid oxide electrode, and preparation method thereof | |
| US7655346B2 (en) | Electrode material and fuel cell | |
| KR101642427B1 (en) | Method for manufacturing anode material for solid oxide fuel cell | |
| JP2003308846A (en) | Perovskite oxide and air electrode for fuel cell | |
| JP3414657B2 (en) | Air electrode materials for nickel-iron based perovskite solid fuel cells | |
| JPH0927330A (en) | Fuel electrode of solid electrolyte fuel cell | |
| CN101572313A (en) | Medium and low temperature solid oxide fuel cell cathode materials and composite cathode materials | |
| JP3381544B2 (en) | Composite air electrode material for low temperature operation solid fuel cells | |
| JP4479039B2 (en) | Electrochemical devices | |
| CN100508259C (en) | Multiple phase electrocatalysis material and preparation method thereof | |
| US7758992B2 (en) | Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrodes in other electrochemical devices | |
| US20060257714A1 (en) | Electrode material and fuel cell | |
| JP2002097021A (en) | High-temperature conductive oxide, fuel cell electrode, and fuel cell using the electrode | |
| JP4119511B2 (en) | Oxide ion conductive material | |
| KR102137988B1 (en) | symmetrical solid oxide fuel cell having perovskite structure, method of manufacturing the same and symmetrical solid oxide electrolyzer cell having the perovskite structure | |
| KR101615694B1 (en) | Method for manufacturing anode material for solid oxide fuel cell | |
| JP2004273143A (en) | Solid oxide fuel cell and air electrode material for solid oxide fuel cell | |
| JPH08130029A (en) | Solid oxide fuel cell and method for manufacturing the same | |
| JP4644326B2 (en) | Lanthanum gallate sintered body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080731 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090731 Year of fee payment: 11 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090731 Year of fee payment: 11 |