JPH01200560A - Electrode material - Google Patents
Electrode materialInfo
- Publication number
- JPH01200560A JPH01200560A JP63023973A JP2397388A JPH01200560A JP H01200560 A JPH01200560 A JP H01200560A JP 63023973 A JP63023973 A JP 63023973A JP 2397388 A JP2397388 A JP 2397388A JP H01200560 A JPH01200560 A JP H01200560A
- Authority
- JP
- Japan
- Prior art keywords
- conductivity
- electrode material
- bulk
- electrode
- oxide
- 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
- 239000007772 electrode material Substances 0.000 title abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 5
- 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 claims description 3
- 230000010287 polarization Effects 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000000446 fuel Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000007784 solid electrolyte Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- 239000011572 manganese Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- -1 oxygen ion Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910052963 cobaltite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
-
- 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
-
- 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)
- Inorganic Compounds Of Heavy Metals (AREA)
- Inert Electrodes (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は′電極材料に関し、特に、固体電解質型燃料電
池（５ｏｌｉｄ ０ｘｉａｅ Ｆｕｅｌ Ｃｅ１１、以
下５ｏｙａと略す）の空気電極材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an electrode material, and particularly to an air electrode material for a solid oxide fuel cell (5 solid oxide fuel cell, hereinafter abbreviated as 5 oya).
５ｏｙａは第１図に例示したように固体′成解質材料２
ｔ−はさんで空気電極１と燃料電極４が取付けられる。5 oya is a solid 'plastite material 2 as illustrated in Fig. 1.
An air electrode 1 and a fuel electrode 4 are attached with the T-apart between them.
なお、３は中間接続子（インコネツタ）、５ｒｉ多孔性
の板又は管状基体である。Note that 3 is an intermediate connector, a 5ri porous plate, or a tubular substrate.
固体電解質材料２としては、酸素イオン導電性を有する
イツトリア安定化ジルコニア（以下Ｙ８Ｚと略す）が多
用されている。空気成極１は高温の酸化雰囲気において
も安定で、高い導電性を有するペロブスカイト型複合酸
化物が、また燃料電極４には、ニッケルなどが使用され
ている。この電池は約１０００ｔｌ：において運転され
る。ペロブスカイト型複合酸化物はＡＥＯ。As the solid electrolyte material 2, yttria-stabilized zirconia (hereinafter abbreviated as Y8Z) having oxygen ion conductivity is often used. The air polarization 1 is made of a perovskite-type composite oxide that is stable even in a high-temperature oxidizing atmosphere and has high conductivity, and the fuel electrode 4 is made of nickel or the like. This cell is operated at approximately 1000 tl. AEO is a perovskite type composite oxide.
（ム、Ｂは金属元素）で表わされ、空気室、極１として
ｕ ＬａＭｎ０．やＬａ（！ｏ０３ の系統のものが
用いられている。この場合Ｌａをムサイト、ＭｎをＢサ
イト元素という。従来はムサイトのＬａの一部をＥｌｒ
＋Ｏａで置換したＬａ １−ｘＡｚＭｎＯＨやＬａ１−
ｘＡｘｏｏｏｓ （Ａ ” １３ｒ Ｉ Ｇａ −、Ｑ
（Ｘ≦α４）で表わされるランタンマンガナイト系（
Ｌａ −Ｍｎ系）、ランタンコバルタイト系（Ｌａ−（
！ｏ系）のものが多用されている。(M, B is a metal element), and as the air chamber and pole 1, u LaMn0. and La(!o03) are used. In this case, La is called mussite and Mn is called B site element. Conventionally, a part of La of mussite was called Elr.
+Oa substituted La 1-xAzMnOH or La1-
xAxoooos (A ” 13r I Ga -, Q
Lanthanum manganite series (X≦α4)
La-Mn series), lanthanum cobaltite series (La-(
! o series) are often used.
ところでＬａ−０ｏ系材料は約１００ＤＣにおいてｌＸ
１０ｍ 〜２Ｘ１０’Ｓ／国（ｓ：ジーメンス＝１／
Ω、コンダクタンス単位）の高い導電率（σ）を示し、
現在公知の空気電極材料の中では最高のものであるが、
１０００℃近辺の高温下ではＹＳＺと反応し、Ｌａ！Ｚ
ｒ０１などの不良溝′亀物質（又は絶縁物質）をＹＳＺ
との接合部に生じさせるため、短期間のうちに電池性能
が低下するという致命的欠点をもっている。従ってｙｓ
ｚを用いるＢＯＦＯの空気電極としては実用性がない。By the way, La-0o material has lX at about 100 DC.
10m ~2X10'S/Country(s:Siemens=1/
Ω, conductance unit) exhibits high conductivity (σ),
Although it is the best among the currently known air electrode materials,
At high temperatures around 1000°C, it reacts with YSZ and La! Z
Remove defective groove material (or insulating material) such as r01 with YSZ
This has the fatal disadvantage of causing battery performance to deteriorate in a short period of time. Therefore, ys
It is not practical as an air electrode for BOFO using Z.
一方Ｌａ−Ｍｎ系の材料はＹＳＺと反応しないが、１０
００℃付近での導電率（σ）が１００８／ｍ程度でＬａ
−ｃｏ系の１／１０と低い欠点がある。On the other hand, La-Mn-based materials do not react with YSZ, but 10
When the conductivity (σ) at around 00℃ is about 1008/m, La
-It has the disadvantage of being 1/10 as low as the co-based type.
′［！！電極材料導電率が低い又は短時間のうちに低下
することは、電池を構成した際の内部抵抗の増大をきた
すもので好ましくない。本発明は高い導電性のＬａ−Ｍ
ｎ系空気藏極上提供し、従来材料における不具合点を克
服しようとするものである。′[! ! It is not preferable for the conductivity of the electrode material to be low or to decrease in a short period of time, as this will lead to an increase in internal resistance when a battery is constructed. The present invention provides highly conductive La-M
The aim is to provide the best n-type air polymer and overcome the drawbacks of conventional materials.
本発明はランタンマンガナイト系のペロプスカイト型腹
合１フ化物においてＬａ １−、ＡＸＭｎ １−、Ｅ、
Ｏ。The present invention relates to a lanthanum manganite-based perovskite-type monofluoride containing La 1-, AXMn 1-, E,
O.
（Ａ＝Ｏａ、 Ｓｒ％ Ｂ＝Ｎｉ、 Ｃｒ、
０ ≦Ｘ≦ （ｌＬ ４．０＜ｙ≦α２５）で表わさ
れる組成を有してなることを特徴とする電極材料である
。(A=Oa, Sr% B=Ni, Cr,
The electrode material is characterized by having a composition expressed by 0≦X≦ (lL 4.0<y≦α25).
前述のように従来のＬａ−Ｍｎ系空気電極材料は”’Ｉ
−ｘＡｘ”ｒ”ｏｓ （ム＝Ｓｒ、Ｃ！ａ、Ｑ≦Ｘ≦１
４）で表わされ、ムサイトのＬａの一部を２価の金属元
素で置換した形のものであった。本発明は上記従来の材
料のＢサイトのＭｎ の一部もＮ１やＯｒ といった遷
移金属元素で置換した形の材料、即ちＬａ１−エＡＸＭ
ｎ１−ｙＢｙＯ８で表わされる従来にない形とすること
によシ前記課題の解決をはかったものである。実験の結
果、ＢはＣｒ、Ｎｉがよく、ｙは後述の実施列から推定
されるよりに０＜ｙ≦１２５とするものである。Ｂとし
てＣＯを用いても導電率は向上するが、ＹＳ、Ｚとの反
応があり、ＹＳＺを用いる５ｏｙａには適用できない。As mentioned above, the conventional La-Mn air electrode material is
-xAx”r”os (Mu=Sr, C!a, Q≦X≦1
4), in which a part of La in muscite was replaced with a divalent metal element. The present invention is a material in which a part of Mn at the B site of the conventional material is replaced with a transition metal element such as N1 or Or, that is, La1-air AXM.
The above-mentioned problem has been solved by creating a non-conventional shape represented by n1-yByO8. As a result of experiments, B is preferably Cr or Ni, and y is set to 0<y≦125, as estimated from the practical sequence described later. Even if CO is used as B, the conductivity is improved, but there is a reaction with YS and Z, so it cannot be applied to 5oya using YSZ.
８０ＩＰＯの空気電極は成子伝導性を有する。 The 80IPO air electrode has seronic conductivity.
これは電極材料のバルクの導電率（オーム抵抗の逆数）
に反映される。更に空気中の酸素を吸着し、電解質側へ
移動させ、捉えた酸素と成極内を流れる電子とを結合さ
せて酸素イオンとなし、成解質へ送シ込むという次の（
１）、（２）、（３）式で表わされる作用も有する。（
１） 、 （２） 、 （３１式を合わせて空気電極反
応と称しているが、この反応の進み易さが電極界面導電
率（’！極外界面抵抗逆数）に反映される。This is the bulk conductivity of the electrode material (the reciprocal of the ohmic resistance)
reflected in Furthermore, the next step is to adsorb oxygen in the air, move it to the electrolyte side, combine the captured oxygen with electrons flowing in the polarization, form oxygen ions, and send them to the electrolyte.
It also has the effects expressed by formulas 1), (2), and (3). (
1), (2), (Equation 31 is collectively referred to as the air electrode reaction, and the ease with which this reaction progresses is reflected in the electrode interface conductivity ('! reciprocal of the outer interface resistance).
０＊（ｒ） ｄ ２０ａｄ （１）
（吸着解ａ）Ｏａｄ表面拡散 （２）（表面拡
散）２０ａｃｌ＋ ４ｅ ３ ２０” （３）
（を荷移動）本発明の方法のとと（Ｌａ の一部
をＳｒ ＋Ｃａで置換した上にＭｎ の一部もＮ１やＯ
ｒで置−換することによって、バルクの導電率（σ）も
界面導電率（σＥ）も向上させることができ、その結果
空気電極の抵抗と分極電位が低下し、ＢＯＦＯの発′成
効率の向上がはかられる。0*(r) d 20ad (1)
(Adsorption solution a) Oad surface diffusion (2) (Surface diffusion) 20acl+ 4e 3 20” (3)
(Cargo transfer) The method of the present invention (part of La is replaced with Sr + Ca, and part of Mn is also replaced with N1 and O
By replacing with r, both the bulk conductivity (σ) and the interfacial conductivity (σE) can be improved, resulting in a decrease in the resistance and polarization potential of the air electrode, and an increase in the BOFO generation efficiency. Improvements can be made.
以下本発明を具体的に説明するに当ってＬａ−Ｍｎ 系
のペロプスカイト型複合酸化物の製造例について説明す
る。In order to specifically explain the present invention, an example of manufacturing a La-Mn based perovskite type composite oxide will be described below.
酸化ランタン： Ｌａ、０１、炭はカルシウム：ｃａｃ
ｏ、 （又は炭酸ストロンチウム： ８ｒＣ！０１ ）
、酸化マンガン： Ｍｎ、Ｏ，および酸化ニッケル：１
ａｉｏ （又は酸化クロム： ０ｒ１０３ ） を所
定量秤量してボールミルに入れ、エチルアルコールを加
えて混合する。これを濾過し、１１０℃で乾燥後１２０
０℃で焼成する。焼成物を１００μｍアンダーとなるよ
う粉砕し、再度１２００℃で焼成してＬａ １ ＋Ｘ○
ａＸＭｎ１−ｙＮｉｙ０３． Ｌａ１−エＯａＸＭｎ１
−ｙＯｒｙＯ，、Ｌａ１−ｚｓｒｚＭｎｌ−ｙＮｉｙ０
３＋ Ｔ、ｉａｉ＋＋ｘＳｒｚＭｎ１−ｙＣｒｙＯ＠な
る組成のペロプスカイト型複合酸化物を得る。（粉末混
合法）
このようにして得た酸化物材料粉末を加圧成形後１４０
０℃で大気中で焼成し、角柱状に切り出し、電極材料と
してのバルクの導電率（σ）を第２図に示すような直流
４端子法によ、！７１０００℃において測定した。第２
図中６は′電極材料、７は白金線、８は電圧計、９は電
流計であシ、記号ｔｉｊ長さ、日は断面積、工は′ＪＬ
流、■は電圧を表わす。この時の導電率（σ）は下記の
式で表わされる。Lanthanum oxide: La, 01, charcoal is calcium: cac
o, (or strontium carbonate: 8rC!01)
, manganese oxide: Mn, O, and nickel oxide: 1
A predetermined amount of aio (or chromium oxide: 0r103) is weighed and placed in a ball mill, and ethyl alcohol is added and mixed. This was filtered and dried at 110°C.
Bake at 0°C. The fired product is crushed to be 100 μm under and fired again at 1200°C to obtain La 1 +X○
aXMn1-yNiy03. La1-E OaXMn1
-yOryO,, La1-zsrzMnl-yNiy0
A perovskite-type composite oxide having a composition of 3+ T,iai++xSrzMn1-yCryO@ is obtained. (Powder mixing method) After pressure molding the oxide material powder obtained in this way,
Sintered in the air at 0°C, cut into a prismatic shape, and measured the bulk electrical conductivity (σ) as an electrode material using the DC 4-terminal method as shown in Figure 2. Measured at 71000°C. Second
In the figure, 6 is 'electrode material, 7 is platinum wire, 8 is voltmeter, 9 is ammeter, symbol tij length, date is cross-sectional area, and engineering is 'JL.
The current and ■ represent the voltage. The electrical conductivity (σ) at this time is expressed by the following formula.
Ｓ −■
また一部の酸化物材料粉末についてはテレピン油でペー
スト化して、別に準備したＹＳｚ（８モル優のＹｔＯ，
を加えて安定化させたＺｒＯ，）焼結体ディスク（１０
Ｗφ×五５鵡ｔ）の片面に塗布し、１１００℃で焼きつ
けた。次にＹＢＺ焼結体ディスクのもう一方の面に白金
ペーストを塗布し、更に参照成極を取シ付け、空気中１
０００℃で焼きつけ、第６図に示すサンプルを得た。第
５図中１０はＹＳＺ規Ｍ体、１１は酸化物Ｓ極、１２は
白金電極、１３は参照電極（白金線）である。この試験
サンプルを用いて交流インピーダンス法により１０００
℃において酸化物電極の界面導電率（σＥ）を、またカ
レントインターラブター法によｆｉ１０００℃における
分極電位（η）を求めた。S - ■ Some of the oxide material powders were made into a paste with turpentine oil and mixed with separately prepared YSz (more than 8 mol of YtO,
ZrO, ) sintered body disk (10
It was coated on one side of a piece of paper (Wφ x 55 cm) and baked at 1100°C. Next, apply platinum paste to the other side of the YBZ sintered disk, attach a reference polarization, and
The sample shown in FIG. 6 was obtained by baking at 000°C. In FIG. 5, 10 is a YSZ standard M body, 11 is an oxide south pole, 12 is a platinum electrode, and 13 is a reference electrode (platinum wire). Using this test sample, 1000 was measured using the AC impedance method.
The interfacial conductivity (σE) of the oxide electrode was determined at °C, and the polarization potential (η) at fi1000 °C was determined by the current interlabator method.
〔実施列コ
実施列１
前述の方法でＬａｇ、。Ｃａ６．、Ｍｎ１−ｙＮｉｙＯ
ｓ およびＬａ、６０ａ６．、Ｍｎ１−ｙＣｒｙｏｌ
を調製し、σおよび一部のサンプルについてσＥお
よびηを測定した。[Implementation Column 1 Lag, by the method described above. Ca6. , Mn1-yNiyO
s and La, 60a6. , Mn1-yCryol
were prepared, and σ and σE and η of some samples were measured.
結果を第１表に示す。Ｌａ６．＠ Ｏａ、、 ＭｎＯ，
のＭｎ の一部をＮ１やＯｒで置換することによって
、σは１、８〜３倍、σＥ は１ｔ５〜１９５倍と飛躍
的に向上する。分極電位はほぼσＥの上昇に追従して低
下する。但し比較例にもあるように余）多鼠の置換はマ
イナス効果となる。The results are shown in Table 1. La6. @Oa,, MnO,
By replacing a part of Mn with N1 or Or, σ is dramatically improved to 1.8 to 3 times, and σE is 1t5 to 195 times. The polarization potential decreases approximately following the increase in σE. However, as shown in the comparative example, the substitution of multiple mice has a negative effect.
第 １ 表
費 電流密度 ２６７ｍム／−ムシ−る値実施例２
Ｌ ａＯ，−８ｒ６．４ Ｍｎ １−ｙＮ ｉ ｙＯｊ
ｅ Ｌ ＩＩＬ６．＠ ８ ｒ６．！Ｍｎ １−ｙＮ
ｉ ｙＯ３およびＬ ａ（１，＠ Ｏａｏ、ｔ Ｍｎ
１−ｙＮ ｉ ｙＯ＠ を調製し、σを測定した。1st Table Current density 267mm/-Mushi-ru value Example 2 L aO, -8r6.4 Mn 1-yN i yOj
e L IIL6. @8 r6. ! Mn 1-yN
i yO3 and L a (1, @ Oao, t Mn
1-yN i yO@ was prepared and σ was measured.
結果を第２表に示す。いずれもＭｎ の一部をＮ１
で置換することによシσの向上が認められた。The results are shown in Table 2. In both cases, a part of Mn is N1
An improvement in σ was observed by replacing with .
第 ２ 表
以上の実施例、特に実施列１よシ、Ｍｎ に対するｌｌ
ｉやＯｒの置換量は２５モル係以下が好ましいことがわ
かる。Table 2 Examples from Table 2 and above, especially row 1, ll for Mn
It can be seen that the amount of substitution of i and Or is preferably 25 molar or less.
また以上の実施列ではＭｎをＮ１またはＯｒ 単独で
置換したもの＼みをあげているが、Ｍｎ をＮｉ、Ｏ
ｒで同時に置換してもはｙ同様の結果が得られる。In addition, in the above implementation series, Mn is replaced with N1 or Or alone, but Mn is replaced with Ni, O
If r is substituted at the same time, the same result as y can be obtained.
本発明によってＬａ−Ｍｎ系戒、臘材料のバルクの導電
率（σ）や界面導電率（σ９）を向上させることができ
、σＢの向上にともなって分極電位を下げることもでき
、従来にない浸れた導電性をもつＬａ−Ｍｎ系の空気電
極材料を得ることが可能となる。The present invention makes it possible to improve the bulk conductivity (σ) and interfacial conductivity (σ9) of La-Mn-based materials, and with the improvement of σB, it is also possible to lower the polarization potential, which is unprecedented. This makes it possible to obtain a La-Mn-based air electrode material with submerged conductivity.
第１図は５ＯＦＯの一悪様の概略図、第２図は直流４端
子法による成極材料のバルクの４成率測定の態様を示す
概略図、第３図は交流インピーダンス法によって界面導
電率（σＥ）を測定するサンプルの構成を示す概略図で
おる。
第２図
第３図Figure 1 is a schematic diagram of one bad aspect of 5OFO, Figure 2 is a schematic diagram showing how to measure the bulk 4 polarization rates of polarization materials using the DC 4-terminal method, and Figure 3 is a diagram showing the interfacial conductivity measured using the AC impedance method. 1 is a schematic diagram showing the configuration of a sample for measuring (σE). Figure 2 Figure 3
Claims (1)
においてＬａ＿１＿−＿ｘＡ＿ｘＭｎ＿１＿−＿ｙＢ＿
ｙＯ＿３（Ａ＝Ｃａ、Ｓｒ、Ｂ＝Ｎｉ、Ｃｒ、０≦ｘ≦
０．４、０＜ｙ≦０．２５）で表わされる組成を有して
なることを特徴とする電極材料。La_1_-_xA_xMn_1_-_yB_ in lanthanum manganite-based perovskite-type composite oxides
yO_3(A=Ca, Sr, B=Ni, Cr, 0≦x≦
0.4, 0<y≦0.25).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63023973A JP2511095B2 (en) | 1988-02-05 | 1988-02-05 | Electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63023973A JP2511095B2 (en) | 1988-02-05 | 1988-02-05 | Electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01200560A true JPH01200560A (en) | 1989-08-11 |
| JP2511095B2 JP2511095B2 (en) | 1996-06-26 |
Family
ID=12125493
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63023973A Expired - Lifetime JP2511095B2 (en) | 1988-02-05 | 1988-02-05 | Electrode material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2511095B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02288159A (en) * | 1989-04-28 | 1990-11-28 | Ngk Insulators Ltd | Ceramic electrode and fuel cell having same |
| EP0577420A1 (en) * | 1992-07-01 | 1994-01-05 | Westinghouse Electric Corporation | A fuel cell containing stable air electrode material |
| EP0593281A2 (en) | 1992-10-14 | 1994-04-20 | Ngk Insulators, Ltd. | Porous lanthanum manganite sintered bodies and solid oxide fuel cells |
| EP0639866A1 (en) * | 1993-08-16 | 1995-02-22 | Westinghouse Electric Corporation | Stable air electrode for high temperature solid oxide electrolyte electrochemical cells |
| JPH08236138A (en) * | 1995-02-28 | 1996-09-13 | Kyocera Corp | Solid oxide fuel cell and method for manufacturing the same |
| EP0902493A1 (en) * | 1997-09-11 | 1999-03-17 | Sulzer Hexis AG | Elektrochemical active element for a solid oxide fuel cell |
| WO2004013925A1 (en) * | 2002-08-01 | 2004-02-12 | The University Court Of The University Of St. Andrews | Perovskite-based fuel cell electrode and membrane |
| JP2020149888A (en) * | 2019-03-14 | 2020-09-17 | 東邦瓦斯株式会社 | Air electrode material, air electrode, and solid oxide fuel cell |
| RU2743341C1 (en) * | 2020-02-03 | 2021-02-17 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт химии силикатов им. В.И. Гребенщикова Российской академии наук (ИХС РАН) | Method for liquid-phase synthesis of nanoceramic materials in system of la2o3-mn2o3-nio for producing cathode electrodes of solid oxide fuel cell |
-
1988
- 1988-02-05 JP JP63023973A patent/JP2511095B2/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02288159A (en) * | 1989-04-28 | 1990-11-28 | Ngk Insulators Ltd | Ceramic electrode and fuel cell having same |
| EP0577420A1 (en) * | 1992-07-01 | 1994-01-05 | Westinghouse Electric Corporation | A fuel cell containing stable air electrode material |
| EP0593281A2 (en) | 1992-10-14 | 1994-04-20 | Ngk Insulators, Ltd. | Porous lanthanum manganite sintered bodies and solid oxide fuel cells |
| EP0593281A3 (en) * | 1992-10-14 | 1994-06-01 | Ngk Insulators Ltd | Porous lanthanum manganite sintered bodies and solid oxide fuel cells |
| EP0639866A1 (en) * | 1993-08-16 | 1995-02-22 | Westinghouse Electric Corporation | Stable air electrode for high temperature solid oxide electrolyte electrochemical cells |
| JPH08236138A (en) * | 1995-02-28 | 1996-09-13 | Kyocera Corp | Solid oxide fuel cell and method for manufacturing the same |
| EP0902493A1 (en) * | 1997-09-11 | 1999-03-17 | Sulzer Hexis AG | Elektrochemical active element for a solid oxide fuel cell |
| US6232009B1 (en) | 1997-09-11 | 2001-05-15 | Sulzer Hexis Ag | Electrochemically active element for a high temperature fuel cell |
| WO2004013925A1 (en) * | 2002-08-01 | 2004-02-12 | The University Court Of The University Of St. Andrews | Perovskite-based fuel cell electrode and membrane |
| CN1322625C (en) * | 2002-08-01 | 2007-06-20 | 圣安德鲁斯大学董事会 | Perovskite-based fuel cell electrode and membrane |
| AU2003248994B2 (en) * | 2002-08-01 | 2008-12-18 | The University Court Of The University Of St. Andrews | Perovskite-based fuel cell electrode and membrane |
| US7504172B2 (en) | 2002-08-01 | 2009-03-17 | The University Court Of The University Of St. Andrews | Perovskite-based fuel cell electrode and membrane |
| JP2020149888A (en) * | 2019-03-14 | 2020-09-17 | 東邦瓦斯株式会社 | Air electrode material, air electrode, and solid oxide fuel cell |
| RU2743341C1 (en) * | 2020-02-03 | 2021-02-17 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт химии силикатов им. В.И. Гребенщикова Российской академии наук (ИХС РАН) | Method for liquid-phase synthesis of nanoceramic materials in system of la2o3-mn2o3-nio for producing cathode electrodes of solid oxide fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2511095B2 (en) | 1996-06-26 |
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