JPH0359953A - Solid electrolyte-type fuel cell - Google Patents
Solid electrolyte-type fuel cellInfo
- Publication number
- JPH0359953A JPH0359953A JP1192720A JP19272089A JPH0359953A JP H0359953 A JPH0359953 A JP H0359953A JP 1192720 A JP1192720 A JP 1192720A JP 19272089 A JP19272089 A JP 19272089A JP H0359953 A JPH0359953 A JP H0359953A
- Authority
- JP
- Japan
- Prior art keywords
- cathode
- solid electrolyte
- fuel cell
- zirconia
- type fuel
- 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
- 239000000446 fuel Substances 0.000 title description 9
- 239000007787 solid Substances 0.000 title description 5
- 239000007784 solid electrolyte Substances 0.000 claims description 10
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 26
- 229910052746 lanthanum Inorganic materials 0.000 description 15
- 229910052712 strontium Inorganic materials 0.000 description 11
- 239000010406 cathode material Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BQENXCOZCUHKRE-UHFFFAOYSA-N [La+3].[La+3].[O-][Mn]([O-])=O.[O-][Mn]([O-])=O.[O-][Mn]([O-])=O Chemical compound [La+3].[La+3].[O-][Mn]([O-])=O.[O-][Mn]([O-])=O.[O-][Mn]([O-])=O BQENXCOZCUHKRE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002078 fully stabilized zirconia Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
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〕
本発明は固体電解質型燃料電池に係り、より詳しく述べ
ると、安定化ジルコニアを固体電解質とする燃料電池の
カソード材料の改良に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to solid electrolyte fuel cells, and more specifically, to improvements in cathode materials for fuel cells using stabilized zirconia as a solid electrolyte.
固体電解質型燃料電池は装置設計の平易性と副生高温の
再利用可能性のゆえに有力な電池エネルギー源の候補と
考えられている。しかしながら、実際に、高性能の固体
電解質型燃料電池を得るた（１）
めには、約１０００℃という高い操作温度に由来する材
料に関する問題を解決しなければならない。Solid oxide fuel cells are considered to be a promising candidate as a battery energy source because of their simplicity in device design and the possibility of reusing high-temperature by-products. However, in order to actually obtain a high-performance solid oxide fuel cell (1), it is necessary to solve problems related to materials resulting from the high operating temperature of about 1000°C.
現段階では固体電解質材料としてイツトリア安定化ジル
コニア（ＹＳＺ）が最も有力とされているが、最も困難
な材料は強力な酸化条件にさらされるカソード材料であ
る。そのカソード材料としては、現在まで、ペロブスカ
イト型の各種複合酸化物が盛んに検討されているが、ス
トロンチウムをドープしたランタンマンガナイトＬａ、
−、Ｓｒ、ｌＭｎＯ３が高い導電率とイツトリア安定化
ジルコニアとの適合性に優れるゆえに好ましいカソード
材料であると考えられている。At present, itria-stabilized zirconia (YSZ) is considered to be the most promising solid electrolyte material, but the most difficult material is the cathode material, which is exposed to strong oxidizing conditions. Until now, various perovskite-type composite oxides have been actively studied as cathode materials, but strontium-doped lanthanum manganite La,
-, Sr, lMnO3 is considered to be a preferred cathode material due to its high conductivity and excellent compatibility with yttria-stabilized zirconia.
第４図に平板型固体電解質型燃料電池を模式的に示すが
、同図中ｌがイツトリア安定化ジルコニア電解質、２が
ランタン系酸化物カソード、３がＮ１／ＺｒＯ２サーメ
ットアノードである。第５図にカソード部分を拡大して
示すが、カソード２側に供給される酸素ガス４は電極粒
子２、ジルコニア電（２）
解質１の三相界面でイオン化して、その酸素イオンがジ
ルコニア電解質■中をアノード３に向って移動する一方
、酸素ガスがイオン化するとき発生した電子はカソード
２から集電体（図示せず）を介して集められる。FIG. 4 schematically shows a flat plate solid electrolyte fuel cell, in which 1 is an yttria-stabilized zirconia electrolyte, 2 is a lanthanum-based oxide cathode, and 3 is an N1/ZrO2 cermet anode. Fig. 5 shows an enlarged view of the cathode part, and the oxygen gas 4 supplied to the cathode 2 side is ionized at the three-phase interface of electrode particles 2, zirconia electrons (2) and solute 1, and the oxygen ions are transferred to the zirconia Electrons generated when the oxygen gas is ionized are collected from the cathode 2 via a current collector (not shown) while moving toward the anode 3 in the electrolyte (2).
このように、カソード２と電解質１は酸素雰囲気下で接
触しており、１０００℃という高温操作条件下ではカソ
ード材料であるランタン系酸化物が電解質であるジルコ
ニアと反応する傾向（下記式（１））があり、この傾向
はランタン系ペロブスカイト型複合酸化物でも同じであ
る（下記式（２））。As described above, the cathode 2 and the electrolyte 1 are in contact with each other in an oxygen atmosphere, and under high-temperature operating conditions of 1000°C, the lanthanum-based oxide that is the cathode material tends to react with the zirconia that is the electrolyte (formula (1) below). ), and this tendency is the same for lanthanum-based perovskite complex oxides (formula (2) below).
％式％（１）
（２）
これらの反応生成物は導電率が低いので、電池の出力を
低下させる原因になる。% Formula % (1) (2) Since these reaction products have low conductivity, they cause a decrease in the output of the battery.
そこで、本発明はランタン系酸化物のジルコニアとの反
応を抑制し、固体電解質型燃料電池の出力低下を防止す
ることを目的とする。Therefore, an object of the present invention is to suppress the reaction of lanthanum-based oxide with zirconia and prevent a decrease in the output of a solid oxide fuel cell.
（３）
〔課題を解決するための手段〕
本発明は、上記課題を解決するために、安定化ジルコニ
アを固体電解質とし、式（Ｌａ、−ｙＳｒｙ） ｌ−１
１−１ｌ〔式中、０≦ｙ≦０．２、Ｑ＜ｘ≦０．２、Ｍ
はＭｎ又はＣＯである〕で表わされる化合物をカソード
とすることを特徴とする固体電解質型燃料電池を提供す
る。(3) [Means for Solving the Problems] In order to solve the above problems, the present invention uses stabilized zirconia as a solid electrolyte, and the formula (La, -ySry) l-1
1-1l [wherein, 0≦y≦0.2, Q<x≦0.2, M
is Mn or CO] as a cathode.
固体電解質としては、イツ） ＩＪアなどを３モル％添
加して安定化した部分安定化ジルコニアから、８モル％
添加して安定化した完全安定化ジルコニアまで、その組
成は特に限定されない。As a solid electrolyte, 8 mol% of partially stabilized zirconia stabilized by adding 3 mol% of IJA etc.
The composition is not particularly limited, including fully stabilized zirconia stabilized by addition.
カソード材料は式（Ｌａ＋ 、Ｓｒ、 ）Ｉ−ＭＭＯ３
で表わされる化合物である。この化合物はＬａの一部を
Ｓｒで置換し又は置換しないＬａＭｎ０．及びＬａＣｏ
Ｏ３においてＬａ又は（Ｌａ 、 Ｓｒ）が化学量論的
に不足している化合物である。Ｌａ又は（Ｌａ 、 Ｓ
ｒ）が不足しているのでＬａ２Ｏ３とＺｒＯ２との反応
が抑制され、最終的にＬａ２ＺｒＯ７の生成が抑制され
る。Ｌａ又は（Ｌａ 、 Ｓｒ）の化学量論的不足が多
いほどＬａ２Ｚｒ０７生成反応抑制の効果は大きいが、
導電率も低下す（４）
るので、Ｘ≦０．２であることが好ましい。ＳｒのＬａ
に対する置換は０≦ｙ≦０．２である。これはＳｒの置
換量が多くなると、導電率が低下するからである。Ｍと
してＭｎ とＣＯは同等である。The cathode material has the formula (La+, Sr, )I-MMO3
It is a compound represented by This compound has LaMn0. and LaCo
It is a compound that is stoichiometrically deficient in La or (La, Sr) in O3. La or (La, S
Since r) is insufficient, the reaction between La2O3 and ZrO2 is suppressed, and finally the production of La2ZrO7 is suppressed. The greater the stoichiometric deficiency of La or (La, Sr), the greater the effect of suppressing the La2Zr07 production reaction.
Since the conductivity also decreases (4), it is preferable that X≦0.2. La of Sr.
The substitution for is 0≦y≦0.2. This is because as the amount of Sr substitution increases, the conductivity decreases. As M, Mn and CO are equivalent.
固体電解質へのカソード材料（Ｌａ 、 Ｓｒ） Ｉ−
Ｘ Ｍｎ３の適用方法は特に限定されず、（Ｌａ 、
Ｓｒ）対Ｍのモル比を調整した上で基本的に（Ｌａ 、
Ｓｒ）Ｍｎ３の適用方法に従うことができる。代表的に
は、Ｌａ２Ｏ３原料、５ｒ２０３原料、Ｍ２Ｏ３原料を
所定のＬａ／Ｍ比に調整し、酸素含有雰囲気中８００〜
１４００℃で焼成して（Ｌａ 、 Ｓｒ）Ｍｎ３で表わ
されるペロブスカイト型化合物を得た後、これを電解質
表面に塗布し、焼成してカソードとする。ランタン源、
ストロンチウム源、マンガン源、コバルト源としては酸
化物、炭酸塩、硝酸塩などを用いることができる。その
他、スパッタ法、プラズマ溶射法などの適用方法も利用
できる。Cathode material (La, Sr) to solid electrolyte I-
The application method of X Mn3 is not particularly limited, and (La,
After adjusting the molar ratio of Sr) to M, basically (La,
Sr)Mn3 application methods can be followed. Typically, La2O3 raw material, 5r203 raw material, and M2O3 raw material are adjusted to a predetermined La/M ratio, and 800~
After firing at 1400° C. to obtain a perovskite compound represented by (La, Sr)Mn3, this is applied to the surface of the electrolyte and fired to form a cathode. lanthanum source,
Oxides, carbonates, nitrates, etc. can be used as the strontium source, manganese source, and cobalt source. Other methods such as sputtering and plasma spraying can also be used.
作用機構は必ずしも明らかではないが、次のよ（５）
うに考えられる。Ｌａ不足の（Ｌａ 、 Ｓｒ） ｌ−
ｘ Ｍｎ３はペロブスカイト型結晶構造の（Ｌａ 、
Ｓｒ）Ｍｎ３のＬａが一部欠除した構造を有し、そのた
め化学量論的化合物と比べて結晶格子が少し小さく （
密度が大きく）なり、またＬａやＭの内部拡散速度も抑
制サレテイル。（Ｌａ 、 Ｓｒ）ＭＯ，とＹ２＋：＋
３／２ｒｏ２の反応はＬａやＭがＺｒＯ□中に拡散して
起きることが知られているので、ＬａやＭの拡散速度が
低下することは（Ｌａ 、 Ｓｒ）ＭＯ３とＹ２Ｏ５／
ＺｒＯ２との反応が抑制されることを意味する。Although the mechanism of action is not necessarily clear, it is thought to be as follows (5). La-deficient (La, Sr) l-
x Mn3 has a perovskite crystal structure (La,
Sr) Mn3 has a structure in which La is partially deleted, so the crystal lattice is slightly smaller than that of a stoichiometric compound (
The density increases) and the internal diffusion rate of La and M is also suppressed. (La, Sr)MO, and Y2+:+
It is known that the 3/2ro2 reaction occurs when La and M diffuse into ZrO□, so the decrease in the diffusion rate of La and M is due to (La, Sr) MO3 and Y2O5/
This means that the reaction with ZrO2 is suppressed.
参考例ｌ
Ｌａ２０３（試薬級） 、５ｒＣＯ３（試薬級）及びＭ
ｎ２０３（試薬級〉を用い、Ｌａ２Ｏ３は市販品を初め
に１０００℃に加熱し室温に急冷したものを用いて、所
定の組成比に調合後、空気中１３００℃で１２時間焼成
してペロブスカイト型酸化物（Ｌａ 、 Ｓｒ） 、−
）ｌ Ｍｎ０３（ｘ ＝ Ｑ 〜０．２〉を作製した。Reference example l La203 (reagent grade), 5rCO3 (reagent grade) and M
n203 (reagent grade) was used, and La2O3 was a commercially available product that was first heated to 1000°C and then rapidly cooled to room temperature. After mixing to a predetermined composition ratio, it was fired in air at 1300°C for 12 hours to produce perovskite-type oxidation. Thing (La, Sr), -
)l Mn03 (x = Q ~0.2>) was prepared.
それから粉砕してＢＥＴ法による表面積値０．２〜０゜
３ｍ”７ｇの粉末とした。It was then ground into a powder with a surface area value of 0.2-0.3 m'' according to the BET method and a weight of 7 g.
（６）
東ソーから人手した８モル％Ｙ２Ｏ３で安定化したジル
コニア（ＢＥＴ表面積値０．２６ｍ’／ ｇ ）を初め
に１４５０℃で３時間加熱してから、（Ｌａ 、 Ｓｒ
） ＋−ＪｎＤ３粉末と混合し、２５００ｋｇ／ＣＩ＋
ｔの圧力で直径１．２ ｃｍのペレットにプレス成形し
た後、空気中１２００〜１３００℃で反応させた。(6) Zirconia (BET surface area value 0.26 m'/g) stabilized with 8 mol% Y2O3 obtained from Tosoh was first heated at 1450°C for 3 hours, and then (La, Sr
) +-Mixed with JnD3 powder, 2500kg/CI+
After press-molding into pellets with a diameter of 1.2 cm at a pressure of t, the pellets were reacted in air at 1200 to 1300°C.
反応後、Ｘ線回折分析により、Ｌａ２Ｚｒ２０７の生成
量を調べた。その結果を第１〜３図に示す。ＬａＭｎＯ
３のＬａの一部をＳｒで置換することによってＬａ２Ｚ
ｒ２０７の生成はいくらか抑制されること、しかしＬａ
のＭｎに対する比率を低減することによってＬａ２Ｚｒ
２０ｔの生成は遅れ、かつ生成速度も抑制され、また特
にその生成の遅れはＬａ量に依存することが見られる。After the reaction, the amount of La2Zr207 produced was determined by X-ray diffraction analysis. The results are shown in Figures 1-3. LaMnO
By replacing part of La in 3 with Sr, La2Z
The production of r207 is somewhat suppressed, but La
By reducing the ratio of La2Zr to Mn
The production of 20t is delayed and the production speed is also suppressed, and in particular, the production delay is seen to depend on the amount of La.
実施例
酸化ランタンＬａ２０３２６．４ｇ（０，０８１モル）
炭酸ストロンチウム５ｒＣＯｓ １．３３ ｇ （０
，００９モル）炭酸マンガンＭｎＣＯ３１１，５ｇ （
０，１モル）これらの原料を乳鉢でよく混合し、８００
℃で３時間焼成した。生成物をよく粉砕し、空気中１３
００（７）
℃で３時間本焼成した。生成物と流動パラフィンのよう
な粘性有機物をよく混合し８モル％イツトリアで安定化
したジルコニア（厚さ２００Ｊ−）表面に塗布し、空気
中１２００〜１３５０℃で１時間焼成しカソードとした
。得られたカソードの組成は（Ｌａ。、。Example Lanthanum oxide La20326.4g (0,081 mol)
Strontium carbonate 5rCOs 1.33 g (0
,009 mol) Manganese carbonate MnCO311.5 g (
0.1 mol) These raw materials were mixed well in a mortar and 800
It was baked at ℃ for 3 hours. Thoroughly grind the product and store it in the air for 13 minutes.
Main firing was performed at 00(7)°C for 3 hours. The product and a viscous organic substance such as liquid paraffin were thoroughly mixed and applied to the surface of zirconia (thickness 200 J-) stabilized with 8 mol% ittria, and baked in air at 1200 to 1350°C for 1 hour to form a cathode. The composition of the obtained cathode was (La.,.
５ｒｏ−＋）。、９Ｍｎ０＋で表わされる。カソードの
厚みは２００−であった。電極面積は１ｃＪとした。5ro-+). , 9Mn0+. The thickness of the cathode was 200-. The electrode area was 1 cJ.
次にＮ１粉とＺｒＯ２粉を重量比で工０／１に混合し、
プラズマ溶射によりジルコニアのカソードと反対側面に
付着させアノードとした。アノード厚さは７０ｊ−であ
った。電極面積は１ ｃｎｆとした。Next, N1 powder and ZrO2 powder were mixed at a weight ratio of 0/1,
It was attached to the opposite side of the zirconia cathode by plasma spraying to form an anode. The anode thickness was 70j-. The electrode area was 1 cnf.
カソードに酸素ガス、アノードに水素ガスを吹きつける
ことにより単セルを形成させ出力を測定した。開放電圧
（ＯＣＶ） ｌｔｌ、３０Ｖ、０．５Ｖ時の電流値は０
．２Ａであり、単位面積あたりの出力は０．１Ｗ ／
ｃｕｔであった。A single cell was formed by blowing oxygen gas to the cathode and hydrogen gas to the anode, and the output was measured. Open circuit voltage (OCV) ltl, 30V, current value at 0.5V is 0
．． 2A, and the output per unit area is 0.1W/
It was a cut.
２４０時間経過後においても、０．１ Ｗ ／ ｃｕｔ
の出力値が得られた。Even after 240 hours, 0.1 W/cut
The output value was obtained.
比較例
原料組成を変えてカソード材料の組成を（Ｌａｏ、 ９
（８）
Ｓｒｏ、 ＋）ＭｎＯ３とする以外は実施例１と全く同
様の操作を行なった。Comparative Example The composition of the cathode material was changed by changing the raw material composition (Lao, 9
(8) The same operation as in Example 1 was performed except that Sro, +)MnO3 was used.
初期の開放電圧（ＯＣＶ）は１．３０Ｖ、出力は０．１
Ｗ／ｃｒＩであったが、２４０時間経過後においては出
力が０．０５Ｗ／ｃ１１１に低下した。Initial open circuit voltage (OCV) is 1.30V, output is 0.1
W/crI, but the output decreased to 0.05W/c111 after 240 hours.
カソードのＸ線回折においては、Ｌａ２Ｚｒ２０７が認
められた。In X-ray diffraction of the cathode, La2Zr207 was observed.
本発明によれば、安定化ジルコニア固体電解質型燃料電
池においてカソード材料の（Ｌａ 、Ｓｒ）ＭｎＯ＋又
ハ（シａ、５ｒ）ＣｏＯ３とジルコニアとの反応が抑制
されるので、不所望なＬａ２Ｚｒ２０７の生成が抑制さ
れ、長期間にわたって所望の電池特性を得ることができ
る。According to the present invention, in a stabilized zirconia solid electrolyte fuel cell, the reaction between the cathode material (La, Sr)MnO+ or Ha(Sia, 5r)CoO3 and zirconia is suppressed, so that the undesired formation of La2Zr207 is suppressed. is suppressed, and desired battery characteristics can be obtained over a long period of time.
第１〜３図は（Ｌａｄ−ｙＳｒｙ ）＋−ＪｎＯｓと８
％Ｙ２Ｏ３／ＺｒＯ２の反応によるＬａ２Ｚｒ２０７の
生成量を示す図、第４〜５図は固体電解質型燃料電池の
模式構造図とその一部拡大図である。
（９）
１・・・固体電解質、 ２・・・カソード、３・・
・アノード、 ４・・・酸素。Figures 1 to 3 show (Lad-ySry)+-JnOs and 8
%Y2O3/ZrO2 reaction, and Figures 4 and 5 are a schematic structural diagram of a solid oxide fuel cell and a partially enlarged diagram thereof. (9) 1... solid electrolyte, 2... cathode, 3...
・Anode, 4...Oxygen.
Claims (1)
＿−＿ｙＳｒ＿ｙ）＿１＿−＿ｘＭＯ＿３〔式中、０≦
ｙ≦０．２、０＜ｘ≦０．２、ＭはＭｎ又はＣｏである
〕で表わされる化合物をカソードとすることを特徴とす
る固体電解質型燃料電池。[Claims] 1. Stabilized zirconia is used as a solid electrolyte, and the formula (La_1
____ySr_y)_1_-_xMO_3 [wherein, 0≦
y≦0.2, 0<x≦0.2, M is Mn or Co] as a cathode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1192720A JPH0359953A (en) | 1989-07-27 | 1989-07-27 | Solid electrolyte-type fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1192720A JPH0359953A (en) | 1989-07-27 | 1989-07-27 | Solid electrolyte-type fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0359953A true JPH0359953A (en) | 1991-03-14 |
Family
ID=16295944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1192720A Pending JPH0359953A (en) | 1989-07-27 | 1989-07-27 | Solid electrolyte-type fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0359953A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5342703A (en) * | 1991-07-19 | 1994-08-30 | Ngk Insulators, Ltd. | Solid electrolyte type fuel cell and method for producing the same |
| JPH06287060A (en) * | 1992-05-11 | 1994-10-11 | Shinagawa Refract Co Ltd | Electrically conductive ceramic composite heat-resistant material composition |
| EP0633619A1 (en) * | 1992-01-13 | 1995-01-11 | Ngk Insulators, Ltd. | Air electrode bodies for solid oxide fuel cells, a process for the production thereof, and a production of solid oxide fuel cells |
| WO1999054946A1 (en) * | 1998-04-21 | 1999-10-28 | Toto Ltd. | Solid electrolyte fuel cell and method of producing the same |
-
1989
- 1989-07-27 JP JP1192720A patent/JPH0359953A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5342703A (en) * | 1991-07-19 | 1994-08-30 | Ngk Insulators, Ltd. | Solid electrolyte type fuel cell and method for producing the same |
| EP0633619A1 (en) * | 1992-01-13 | 1995-01-11 | Ngk Insulators, Ltd. | Air electrode bodies for solid oxide fuel cells, a process for the production thereof, and a production of solid oxide fuel cells |
| US5453330A (en) * | 1992-01-13 | 1995-09-26 | Ngk Insulators, Ltd. | Air electrode bodies for solid oxide fuel cells, a process for the production thereof, and a production of solid oxide fuel cells |
| JPH06287060A (en) * | 1992-05-11 | 1994-10-11 | Shinagawa Refract Co Ltd | Electrically conductive ceramic composite heat-resistant material composition |
| JP2541726B2 (en) * | 1992-05-11 | 1996-10-09 | 品川白煉瓦株式会社 | Ceramic composite conductive heat resistant material composition |
| WO1999054946A1 (en) * | 1998-04-21 | 1999-10-28 | Toto Ltd. | Solid electrolyte fuel cell and method of producing the same |
| US6692855B1 (en) | 1998-04-21 | 2004-02-17 | Toto Ltd. | Solid electrolyte type fuel cell and method of producing the same |
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