JP2008041306A - Power generation cell, and solid electrolyte fuel cell with power generation cell incorporated therein - Google Patents
Power generation cell, and solid electrolyte fuel cell with power generation cell incorporated therein Download PDFInfo
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この発明は、発電性能を一層向上させることができる発電セルおよびその発電セルを組み込んだ固体電解質形燃料電池に関するものである。 The present invention relates to a power generation cell capable of further improving power generation performance and a solid oxide fuel cell incorporating the power generation cell.
固体電解質形燃料電池は、酸化物からなる固体電解質の片面に空気極を積層し、固体電解質のもう一方の片面に燃料極を積層してなる構造を有している発電セルと、この発電セルの空気極の外側に空気極集電体を積層させ、一方、発電セルの燃料極の外側に燃料極集電体を積層させ、前記空気極集電体の外側に空気極集電体側セパレータを積層させ、前記燃料極集電体の外側に燃料極集電体側セパレータを積層させた基本構造を有している。
かかる基本構造を有する固体電解質形燃料電池は、酸化剤ガス（空気または酸素）を空気極集電体側セパレータに接続して設けられたパイプなどからなる空気供給通路を通して空気極集電体に供給し、同時に、燃料ガス（水素リッチガス）を燃料極集電体側セパレータに接続して設けられたパイプなどからなる燃料供給通路を通して燃料集電体に供給して運転する。
A solid electrolyte fuel cell includes a power generation cell having a structure in which an air electrode is stacked on one side of a solid electrolyte made of an oxide and a fuel electrode is stacked on the other side of the solid electrolyte, and the power generation cell An air electrode current collector is laminated outside the air electrode current collector, while a fuel electrode current collector is laminated outside the fuel electrode of the power generation cell, and an air electrode current collector side separator is arranged outside the air electrode current collector. It has a basic structure in which a fuel electrode current collector separator is stacked on the outside of the fuel electrode current collector.
A solid oxide fuel cell having such a basic structure supplies an oxidant gas (air or oxygen) to an air electrode current collector through an air supply passage formed of a pipe or the like provided by connecting to an air electrode current collector side separator. At the same time, fuel gas (hydrogen-rich gas) is supplied to the fuel current collector through a fuel supply passage made of a pipe or the like connected to the anode current collector separator.
前記固体電解質形燃料電池の発電セルを構成する固体電解質として、ランタンガレート系酸化物イオン伝導体を用いることが知られており、このランタンガレート系酸化物イオン伝導体は、一般式：Ｌａ1-X ＳｒX Ｇａ1-Y-Z ＭｇY ＡZ Ｏ3（式中、Ａ＝Ｃｏ、Ｆｅ、Ｎｉ、Ｃｕの１種または２種以上、Ｘ＝０．０５〜０．３、Ｙ＝０〜０．２９、Ｚ＝０．０１〜０．３、Ｙ＋Ｚ＝０．０２５〜０．３）で表される酸化物イオン伝導体であることが知られている（特許文献１参照）。 It is known that a lanthanum gallate-based oxide ion conductor is used as a solid electrolyte constituting a power generation cell of the solid electrolyte fuel cell. The lanthanum gallate-based oxide ion conductor has a general formula: La 1− X Sr X Ga 1-YZ Mg Y a Z O 3 ( where, a = Co, Fe, Ni , Cu 1 or more kinds of, X = 0.05~0.3, Y = 0~0 . 29, Z = 0.01 to 0.3, Y + Z = 0.025 to 0.3) is known (see Patent Document 1).
また、前記燃料極は、一般式：Ｃｅ1-mＢmＯ2、（式中、ＢはＳｍ、Ｌａ、Ｇｄ、Ｙ、Ｃａの１種または２種以上、ｍは０＜ｍ≦０．４）で表されるＢ（ただし、ＢはＳｍ、Ｌａ、Ｇｄ、Ｙ、Ｃａの１種または２種以上を示す。以下、同じ）ドープされたセリア粒とニッケル粒とで構成された多孔質焼結体からなることが知られており、この多孔質焼結体はニッケル粒が相互に焼結して骨格構造を形成し、その骨格構造を有する多孔質ニッケルの表面に０．１〜２μｍの粒径を有するＢドープされたセリア粒がネットワーク構造を形成して付着した構造を有していることも知られている。
さらに、空気極はコバルタイト化合物［例えば、（Ｂａ、Ｌａ）ＣｏＯ3、（Ｓｍ、Ｓｒ）ＣｏＯ3など］や酸化マンガン化合物［例えば、（Ｌａ、Ｓｒ）ＭｎＯ3など］のセラミックスで構成されている（特許文献２参照）。
The fuel electrode has a general formula: Ce 1-m B m O 2 , wherein B is one or more of Sm, La, Gd, Y, and Ca, and m is 0 <m ≦ 0. 4) B represented by B (where B represents one or more of Sm, La, Gd, Y, and Ca. The same applies hereinafter) Porous material composed of doped ceria grains and nickel grains This porous sintered body is known to be composed of a sintered body, and nickel particles are sintered together to form a skeleton structure, and the surface of the porous nickel having the skeleton structure has a thickness of 0.1 to 2 μm. It is also known that B-doped ceria grains having a grain size of 1 have a structure in which a network structure is formed and adhered.
Further, the air electrode is composed of a ceramic of a cobaltite compound [eg (Ba, La) CoO 3 , (Sm, Sr) CoO 3 etc.] or a manganese oxide compound [eg (La, Sr) MnO 3 etc.]. (See Patent Document 2).
一方、燃料極集電体は、一般に、Ｎｉメッシュ、Ｎｉフェルト、発泡Ｎｉを含むＮｉの多孔質体、さらに白金メッシュなどで構成されている。さらに空気極集電体は、一般に、Ａｇメッシュ、Ａｇフェルト、発泡ＡｇなどのＡｇ多孔質体、さらにＡｇ以外の金属からなるメッシュ、フェルト、発泡金属の表面をＡｇで被覆したＡｇ被覆多孔質金属体などが使用されるようになっている（特許文献３参照）。 On the other hand, the fuel electrode current collector is generally composed of Ni mesh, Ni felt, Ni porous material including foamed Ni, platinum mesh and the like. Further, the air electrode current collector is generally an Ag-coated porous metal in which the surface of an Ag porous body such as Ag mesh, Ag felt, or foamed Ag, and a mesh, felt, or foamed metal made of a metal other than Ag is coated with Ag. The body etc. are used (refer patent document 3).
さらに、前記固体電解質形燃料電池の空気極集電体側セパレータおよび燃料極集電体側セパレータは、通常、高温耐食性に優れたＳＵＳ４３０などのステンレス鋼で構成されているが、空気極集電体側セパレータの表面は特に酸化され易く、空気極集電体側セパレータの表面が酸化されて空気極集電体との接触抵抗が大きくなって起電力が大きく消耗し、それによって発電効率が大きく低下するところから、一般に、空気極集電体側セパレータの表面にはＡｇメッキ層が形成されるようになってきた（特許文献４参照）。 Furthermore, the air electrode current collector side separator and the fuel electrode current collector side separator of the solid electrolyte fuel cell are usually made of stainless steel such as SUS430 having excellent high temperature corrosion resistance. Since the surface is particularly easily oxidized, the surface of the air electrode current collector separator is oxidized, the contact resistance with the air electrode current collector is increased, the electromotive force is greatly consumed, and thereby the power generation efficiency is greatly reduced. In general, an Ag plating layer has been formed on the surface of the air electrode current collector separator (see Patent Document 4).
かかる構成を有する固体電解質形燃料電池は、空気極の表面上では、酸素分子から酸素原子への解離反応が起こり、空気極集電体より酸素原子が電子を受け取り、電子を受け取った酸素原子はイオン化された混合伝導体である空気極の極中あるいは電極上を移動し、電解質中へ移動していく。その際に、酸素分子から酸素原子への解離反応は、酸素分子が空気極との衝突により空気極の電極上全面で比較的起こりやすいが、イオン化反応は電子が供給されないと起こらないため、空気極集電体と空気極が接触している付近において頻繁に起こりやすいと言われている。したがって、空気極集電体と空気極との接触面積の大きい固体電解質形燃料電池であるほど発電性能を高めることができることから、空気極集電体と空気極との接触面積を高めるべくいろいろな工夫がなされており、その中でも空気極集電体の空気極に接する側の表面にＡｇ粉末焼結層を形成することにより発電性能を向上させることが提案されている（特許文献５参照）。
In the solid oxide fuel cell having such a configuration, on the surface of the air electrode, a dissociation reaction from oxygen molecules to oxygen atoms occurs, the oxygen atoms receive electrons from the air electrode current collector, and the oxygen atoms that have received the electrons are It moves in or on the air electrode, which is an ionized mixed conductor, and moves into the electrolyte. At this time, the dissociation reaction from oxygen molecules to oxygen atoms occurs relatively easily on the entire surface of the air electrode due to collision of the oxygen molecules with the air electrode, but the ionization reaction does not occur unless electrons are supplied. It is said that it is likely to occur frequently in the vicinity where the electrode current collector and the air electrode are in contact. Therefore, since the power generation performance can be improved as the solid electrolyte fuel cell has a larger contact area between the air electrode current collector and the air electrode, there are various ways to increase the contact area between the air electrode current collector and the air electrode. A device has been devised, and among them, it has been proposed to improve the power generation performance by forming an Ag powder sintered layer on the surface of the air electrode current collector that is in contact with the air electrode (see Patent Document 5).
空気極集電体の空気極に接する側の表面にＡｇ粉末焼結層を形成することにより発電性能は向上するものの、さらに一層の発電性能が優れた固体電解質形燃料電池が求められている。 Although the power generation performance is improved by forming an Ag powder sintered layer on the surface of the air electrode current collector that is in contact with the air electrode, there is a need for a solid oxide fuel cell with even greater power generation performance.
そこで、本発明者等は、上述のような観点から、さらに一層の発電性能が優れた固体電解質形燃料電池を開発すべく研究を行った。その結果、
（イ）Ｌａ1-X ＳｒX Ｇａ1-Y-Z ＭｇY ＣｏZ Ｏ3（ただし、Ｘ＝０．０５〜０．３、Ｙ＝０〜０．２９、Ｚ＝０．０１〜０．３、Ｙ＋Ｚ＝０．０２５〜０．３）で表される酸化物イオン伝導体からなる固体電解質の片面に、コバルタイト化合物のセラミックスで構成されている空気極を積層し、前記固体電解質のもう一方の片面に一般式：Ｃｅ1-mＳｍmＯ2、（ｍは０＜ｍ≦０．４）で表されるＳｍドープされたセリア粒とニッケル粒とで構成された多孔質焼結体からなる燃料極を積層してなる構造を有している発電セルと、この発電セルの空気極の外側にＡｇ多孔質からなる空気極集電体を積層させ、一方、発電セルの燃料極の外側にＮｉ多孔質からなる燃料極集電体を積層させ、前記空気極集電体の外側に空気極集電体側セパレータを積層させ、前記燃料極集電体の外側に燃料極集電体側セパレータを積層させた基本構造を有している従来の固体電解質形燃料電池において、前記発電セルの空気極の表面に、平均粒径：０．０５〜２μｍの微細Ａｇ粒子が１〜２０面積％均一分散して付着している固体酸化物形燃料電池は、従来の空気極集電体の空気極に接する側の表面にＡｇ粉末焼結層を形成した複合層からなる空気極集電体を組み込んだ引用文献５記載の従来の固体電解質形燃料電池よりも発電性能が一層向上する、
（ロ）前記発電セルを構成する空気極は、コバルタイト化合物で構成されていることが好ましく、コバルタイト化合物の中でも（Ｂａ、Ｌａ）ＣｏＯ3または（Ｓｍ、Ｓｒ）ＣｏＯ3であることが一層好ましい、などのという研究結果が得られたのである。
In view of the above, the present inventors have conducted research to develop a solid oxide fuel cell with further excellent power generation performance. as a result,
(B) La 1-X Sr X Ga 1-YZ Mg Y Co Z O 3 ( provided that, X = 0.05~0.3, Y = 0~0.29 , Z = 0.01~0.3, Y + Z = 0.025-0.3) is laminated on one side of a solid electrolyte made of an oxide ion conductor, and the other side of the solid electrolyte is laminated with an air electrode made of a ceramic of a cobaltite compound. A fuel comprising a porous sintered body composed of Sm-doped ceria grains and nickel grains represented by the general formula: Ce 1-m Sm m O 2 (m is 0 <m ≦ 0.4) A power generation cell having a structure in which electrodes are stacked, and an air electrode current collector made of Ag porous are stacked outside the air electrode of the power generation cell, while Ni is formed outside the fuel electrode of the power generation cell. A porous fuel electrode current collector is laminated and an air electrode current collector separator is stacked outside the air electrode current collector. In a conventional solid oxide fuel cell having a basic structure in which a fuel electrode current collector-side separator is laminated on the outside of the fuel electrode current collector, average particles are formed on the air electrode surface of the power generation cell. A solid oxide fuel cell in which fine Ag particles having a diameter of 0.05 to 2 μm are uniformly dispersed and adhered is 1 to 20 area%. The Ag is formed on the surface of the conventional air electrode current collector in contact with the air electrode. The power generation performance is further improved than the conventional solid oxide fuel cell described in Citation 5, which incorporates an air electrode current collector composed of a composite layer in which a powder sintered layer is formed.
(B) The air electrode constituting the power generation cell is preferably composed of a cobaltite compound, and among the cobaltite compounds, (Ba, La) CoO 3 or (Sm, Sr) CoO 3 is more preferable. The results of the research were obtained.
この発明は、かかる研究結果に基づいてなされたものであって、
（１）一般式：Ｌａ1-X ＳｒX Ｇａ1-Y-Z ＭｇY ＣｏZ Ｏ3（ただし、Ｘ＝０．０５〜０．３、Ｙ＝０〜０．２９、Ｚ＝０．０１〜０．３、Ｙ＋Ｚ＝０．０２５〜０．３）で表される酸化物イオン伝導体からなる固体電解質の片面に、コバルタイト化合物からなる空気極を積層し、前記固体電解質のもう一方の片面に一般式：Ｃｅ1-mＳｍmＯ2、（ｍは０＜ｍ≦０．４）で表されるＳｍドープされたセリア粒とニッケル粒とで構成された多孔質焼結体からなる燃料極を積層してなる構造を有する発電セルであって、前記発電セルの空気極は、その表面に平均粒径：０．０５〜２μｍの微細Ａｇ粒子が１〜２０面積％均一分散して付着している微細Ａｇ粒子付着空気極である固体酸化物形燃料電池の発電セル、
（２）前記コバルタイト化合物のセラミックスで構成されている空気極は、（Ｂａ、Ｌａ）ＣｏＯ3または（Ｓｍ、Ｓｒ）ＣｏＯ3である前記（１）記載の固体酸化物型燃料電池の発電セル、
（３）前記（１）または（２）記載の固体酸化物形燃料電池の発電セルにおける微細Ａｇ粒子付着空気極の外側にＡｇ多孔質からなる空気極集電体を積層させ、一方、前記発電セルの燃料極の外側にＮｉ多孔質からなる燃料極集電体を積層させ、前記空気極集電体の外側に空気極集電体側セパレータを積層させ、前記燃料極集電体の外側に燃料極集電体側セパレータを積層させてなる固体酸化物形燃料電池、に特徴を有するものである。
The present invention has been made based on the results of such research,
(1) General formula: La 1-X Sr X Ga 1-YZ Mg Y Co Z O 3 ( provided that, X = 0.05~0.3, Y = 0~0.29 , Z = 0.01~0 .3, Y + Z = 0.025 to 0.3), an air electrode made of a cobaltite compound is laminated on one side of a solid electrolyte made of an oxide ion conductor, and the other side of the solid electrolyte is generally used. A fuel electrode comprising a porous sintered body composed of Sm-doped ceria grains and nickel grains represented by the formula: Ce 1-m Sm m O 2 (m is 0 <m ≦ 0.4). A power generation cell having a laminated structure, wherein the air electrode of the power generation cell has fine Ag particles with an average particle size of 0.05 to 2 μm uniformly dispersed and adhered to the surface thereof. A solid oxide fuel cell power generation cell, which is an air electrode with fine Ag particles attached,
(2) The power generation cell of the solid oxide fuel cell according to (1), wherein the air electrode made of the ceramic of the cobaltite compound is (Ba, La) CoO 3 or (Sm, Sr) CoO 3 .
(3) The air electrode current collector made of Ag porous is laminated outside the air electrode attached with fine Ag particles in the power generation cell of the solid oxide fuel cell according to (1) or (2), while the power generation A fuel electrode current collector made of porous Ni is laminated outside the fuel electrode of the cell, an air electrode current collector separator is laminated outside the air electrode current collector, and a fuel is formed outside the fuel electrode current collector. The present invention is characterized by a solid oxide fuel cell formed by laminating a pole current collector side separator.
この発明の発電セルを構成する微細Ａｇ粒子付着空気極の表面に均一分散して付着している微細Ａｇ粒子の平均粒径は０．０５μｍ未満ではＡｇ粒子が微細すぎて空気極内部にＡｇ粒子が入り込み、空気極集電体との接触点が減少するので好ましくなく、一方、微細Ａｇ粒子の平均粒径は２μｍを越えると、Ａｇ粒子が粗すぎて空気極集電体との接触点が減少するので好ましくない。したがって、微細Ａｇ粒子付着空気極の表面に均一分散して付着している微細Ａｇ粒子の平均粒径を０．０５〜２μｍに定めた。
さらに、前記微細Ａｇ粒子付着空気極の表面に付着して均一分散している微細Ａｇ粒子の分散率は１面積％未満では、空気極集電体との接触点が少なく、したがって抵抗が大きくなるので好ましくなく、一方、前記微細Ａｇ粒子付着空気極の表面に付着して均一分散している微細Ａｇ粒子の分散率が２０面積％を越えると、Ａｇ粒子同士が結合し、空気極の表面積が小さくなるために電極としての活性が劣るのでので好ましくない。したがって、微細Ａｇ粒子の空気極の表面に付着して均一分散している分散率を１〜２０面積％に定めた。一層好ましい範囲は５〜１０面積％である。
If the average particle size of the fine Ag particles adhering to the fine Ag particle adhering air electrode constituting the power generation cell of this invention is less than 0.05 μm, the Ag particles are too fine and the Ag particles are inside the air electrode. And the contact point with the air electrode current collector decreases, which is not preferable. On the other hand, if the average particle size of the fine Ag particles exceeds 2 μm, the Ag particles are too coarse and the contact point with the air electrode current collector is not good. Since it decreases, it is not preferable. Therefore, the average particle diameter of the fine Ag particles uniformly dispersed on the surface of the fine Ag particle-attached air electrode is set to 0.05 to 2 μm.
Further, when the dispersion ratio of the fine Ag particles adhering to and uniformly dispersed on the surface of the fine Ag particle-attached air electrode is less than 1 area%, the number of contact points with the air electrode current collector is small, and thus the resistance increases. On the other hand, if the dispersion ratio of the fine Ag particles adhering to the surface of the fine Ag particle adhering air electrode and uniformly dispersed exceeds 20 area%, the Ag particles are bonded to each other, and the surface area of the air electrode is reduced. Since it becomes small and the activity as an electrode is inferior, it is not preferable. Therefore, the dispersion ratio at which fine Ag particles adhere to the surface of the air electrode and are uniformly dispersed is set to 1 to 20 area%. A more preferable range is 5 to 10 area%.
この発明の発電セルを構成する表面に平均粒径：０．０５〜２μｍの微細Ａｇ粒子が１〜２０面積％均一分散して付着させた微細Ａｇ粒子付着空気極を作製するには、通常の空気極の表面に平均粒径：５〜１５ｎｍの超微細Ａｇ粉末をエタノールに懸濁させたＡｇコロイドを塗布し、乾燥させたのち温度：３００〜８００℃で焼成することにより製造することができる。
In order to produce a fine Ag particle-attached air electrode in which fine Ag particles having an average particle diameter of 0.05 to 2 μm are uniformly dispersed and adhered to the surface constituting the power generation cell of this invention, It can be produced by applying Ag colloid obtained by suspending ultrafine Ag powder having an average particle diameter of 5 to 15 nm in ethanol on the surface of the air electrode, drying the powder, and then baking at a temperature of 300 to 800 ° C. .
この発明の固体電解質形燃料電池を構成する空気極集電体はＡｇ多孔質からなり、このＡｇ多孔質は、Ａｇ繊維を圧縮して形成したＡｇフェルト、Ａｇよりも高温強度に優れた金属または合金からなる金属繊維の表面にＡｇメッキしたＡｇメッキ繊維を圧縮して形成したＡｇメッキフェルト、Ａｇ細線からなるＡｇメッシュ層、Ａｇよりも高温強度に優れた金属または合金からなる金属細線の表面にＡｇメッキしたＡｇメッキ細線からなるＡｇメッキメッシュ、発泡Ａｇなどを含むものである。 The air electrode current collector constituting the solid oxide fuel cell of the present invention is composed of Ag porous, which is Ag felt formed by compressing Ag fibers, metal superior in high-temperature strength than Ag, or Ag plating felt formed by compressing Ag-plated Ag-plated fiber on the surface of metal fiber made of alloy, Ag mesh layer made of Ag fine wire, surface of metal fine wire made of metal or alloy having higher temperature strength than Ag It includes an Ag-plated mesh made of Ag-plated Ag-plated fine wires, foamed Ag, and the like.
この発明の固体電解質形燃料電池を構成する燃料極集電体はＮｉ多孔質体からなり、このＮｉ多孔質体は、Ｎｉ繊維を圧縮して形成したＮｉフェルト、Ｎｉよりも高温強度に優れた金属または合金からなる金属繊維の表面にＮｉメッキしたＮｉメッキ繊維を圧縮して形成したＮｉメッキフェルト、Ｎｉ細線からなるＮｉメッシュ層、Ｎｉよりも高温強度に優れた金属または合金からなる金属細線の表面にＮｉメッキしたＮｉメッキ細線からなるＮｉメッキメッシュ、発泡Ｎｉなどを含むものである。
The anode current collector constituting the solid oxide fuel cell of the present invention is composed of a Ni porous body, and this Ni porous body is superior to Ni felt formed by compressing Ni fibers, and high temperature strength than Ni. Ni-plated felt formed by compressing Ni-plated Ni-plated fiber on the surface of metal fiber made of metal or alloy, Ni mesh layer made of Ni fine wire, metal fine wire made of metal or alloy superior in strength at high temperature than Ni It includes Ni-plated mesh made of Ni-plated fine wires plated with Ni, foamed Ni, and the like.
この発明の微細Ａｇ粒子付着空気極を有する発電セルを組み込んだ固体酸化物形燃料電池は、発電性能を一層高めることができ、固体酸化物形燃料電池産業の発展におおいに貢献しうるものである。 The solid oxide fuel cell incorporating the power generation cell having the fine Ag particle-attached air electrode according to the present invention can further improve the power generation performance, and can greatly contribute to the development of the solid oxide fuel cell industry. .
実施例１
原料粉末として、Ｌａ2Ｏ3、ＳｒＣＯ3、Ｇａ2Ｏ3、ＭｇＯ、ＣｏＯの各粉末を用意し、これら原料粉末を（Ｌａ０．８Ｓｒ０．２）（Ｇａ０．８Ｍｇ０．１５Ｃｏ０．０５）Ｏ３となるように秤量し、良く混合した後、１１００℃で予備焼成し、得られた仮焼体を粉砕し、通常のバインダー、溶剤などを加えてボールミルで粉砕することによりスラリーを作製し、このスラリーをドクターブレード法によりグリーンシートに成形した。この成形したグリーンシートを空気中で十分に乾燥させ、所定の寸法に切り出してこれを１４５０℃で燒結し、直径：１２０ｍｍ、厚さ：０．２ｍｍの寸法を有する燒結体からなる固体電解質を作製した。
Example 1
As raw material powders, La 2 O 3 , SrCO 3 , Ga 2 O 3 , MgO, and CoO powders were prepared, and these raw material powders were (La 0.8 Sr 0.2 ) (Ga 0.8 Mg 0.15 Co 0.05 ) O 3 , weighed and mixed well, pre-fired at 1100 ° C., pulverized calcined body, added normal binder, solvent, etc. and pulverized with a ball mill A slurry was prepared by the above method, and this slurry was formed into a green sheet by the doctor blade method. The green sheet thus formed is sufficiently dried in the air, cut into predetermined dimensions, and sintered at 1450 ° C. to produce a solid electrolyte comprising a sintered body having a diameter of 120 mm and a thickness of 0.2 mm. did.
このようにして得られた固体電解質の片面にＮｉと（Ｃｅ0.8Ｓｍ0.2）Ｏ2の体積比が６：４になるように混合したＮｉＯと（Ｃｅ0.8Ｓｍ0.2）Ｏ2の混合粉末を１１００℃で焼付けることにより厚さ：０．０３ｍｍの燃料極を形成し、さらに前記固体電解質の反対側の片面に厚さ：０．０３ｍｍの（Ｂａ、Ｌａ）ＣｏＯ3を１０００℃で焼付け、空気極を形成することにより発電セルを作製した。
さらに、平均粒径：１０ｎｍのＡｇ超微粉末をエタノールに添加して懸濁させたＡｇコロイドを用意し、これを発電セルの空気極の表面に塗布し乾燥させたのち、得られたＡｇコロイド塗布層を表１に示される温度で焼成することにより表１に示される平均粒径の微細Ａｇ粒子が表１に示される面積率で空気極の表面に均一分散して付着した微細Ａｇ粒子付着空気極を有する発電セルを作製した。
A mixed powder of NiO and (Ce 0.8 Sm 0.2 ) O 2 mixed so that the volume ratio of Ni and (Ce 0.8 Sm 0.2 ) O 2 is 6: 4 is 1100 on one side of the solid electrolyte thus obtained. A fuel electrode having a thickness of 0.03 mm is formed by baking at a temperature of 0.03 mm, and (Ba, La) CoO 3 having a thickness of 0.03 mm is baked at 1000 ° C. on one side opposite to the solid electrolyte. A power generation cell was fabricated by forming a pole.
Further, an Ag colloid in which Ag ultrafine powder having an average particle size of 10 nm is added and suspended in ethanol is prepared, and this is applied to the surface of the air electrode of the power generation cell and dried, and then the obtained Ag colloid is obtained. By depositing the coating layer at the temperature shown in Table 1, the fine Ag particles having the average particle size shown in Table 1 are uniformly dispersed and adhered to the surface of the air electrode at the area ratio shown in Table 1. A power generation cell having an air electrode was produced.
さらに、燃料極集電体として市販のＮｉフェルトを用意し、さらに空気極集電体として市販の純Ａｇフェルトを用意し、さらに厚さ：３ｍｍのＳＵＳ３０４ステンレス鋼板に機械加工を施して溝を形成し、燃料極側セパレータおよび空気極側セパレータを作製し用意した。
Furthermore, a commercially available Ni felt is prepared as a fuel electrode current collector, a commercially available pure Ag felt is prepared as an air electrode current collector, and a groove is formed by machining a SUS304 stainless steel plate having a thickness of 3 mm. A fuel electrode side separator and an air electrode side separator were prepared and prepared.
このようにして作製した微細Ａｇ粒子付着発電セルにおける燃料極側に燃料極集電体であるＮｉフェルトを積層し、さらに微細Ａｇ粒子が表面に均一に付着した微細Ａｇ粒子付着空気極側に前記純Ａｇフェルトからなる空気極集電体を積層させ、さらに、これら燃料極集電体および空気極集電体の上に先に用意したセパレータを積層させて本発明固体電解質燃料電池１〜１１、比較固体電解質燃料電池１〜４を作製した。 In the thus produced fine Ag particle-attached power generation cell, Ni felt as a fuel electrode current collector is laminated on the fuel electrode side, and the fine Ag particle-attached air electrode side on which fine Ag particles are uniformly attached to the surface. The present invention solid electrolyte fuel cells 1 to 11 are laminated by laminating an air electrode current collector made of pure Ag felt, and further laminating the separator prepared previously on the fuel electrode current collector and the air electrode current collector. Comparative solid electrolyte fuel cells 1 to 4 were produced.
このようにして得られた本発明固体電解質燃料電池１〜１１、比較固体電解質燃料電池１〜４を７５０℃に保持しながら燃料ガスとして乾燥水素ガスを５ｃｃ／ｍｉｎ／ｃｍ２の流量で流し、酸化剤ガスとして空気を流し運転し、本発明固体電解質燃料電池１〜１１、比較固体電解質燃料電池１〜４について電流密度：５００ｍＡ／ｃｍ２における電圧および起電力を測定し、その結果を表１に示すことにより発電性能を評価した。 While maintaining the solid electrolyte fuel cells 1 to 11 of the present invention and the comparative solid electrolyte fuel cells 1 to 4 thus obtained at 750 ° C., dry hydrogen gas was allowed to flow at a flow rate of 5 cc / min / cm 2 as a fuel gas, It was operated by flowing air as an oxidant gas, and the voltage and electromotive force at a current density of 500 mA / cm 2 were measured for the solid electrolyte fuel cells 1 to 11 of the present invention and the comparative solid electrolyte fuel cells 1 to 4, and the results are shown in Table 1. The power generation performance was evaluated by showing.
従来例１
市販の純銀フェルトを９１０℃に加熱したのち純銀超微粉末層の上に載置することにより純銀フェルトの片面に純銀超微粉末燒結層を形成し、純銀フェルトおよび純銀超微粉末燒結層の複合層からなる空気極集電体を作製し用意した。この空気極集電体を実施例１で作製した発電セルにおける（Ｂａ、Ｌａ）ＣｏＯ3からなる空気極側に積層し、さらにこの発電セルのＮｉと（Ｃｅ0.8Ｓｍ0.2）Ｏ2からなる燃料極側に市販のＮｉフェルトからなる燃料極集電体を積層させ、さらにセパレータを前記空気極集電体および燃料極集電体の上に積層させることにより従来固体電解質燃料電池１を作製した。
このようにして得られた従来固体電解質燃料電池１を７５０℃に保持しながら実施例１と同じ条件で燃料ガスとして乾燥水素ガスを流し、酸化剤ガスとして空気を流し、従来固体電解質燃料電池１について電流密度：５００ｍＡ／ｃｍ２における電圧および起電力を測定し、その結果を表１に示すことにより発電性能を評価した。
Conventional Example 1
A commercially available pure silver felt is heated to 910 ° C. and then placed on the pure silver ultrafine powder layer to form a pure silver ultrafine powder sintered layer on one side of the pure silver felt, and a composite of pure silver felt and pure silver ultrafine powder sintered layer A cathode current collector made of layers was prepared and prepared. This air electrode current collector is laminated on the air electrode side made of (Ba, La) CoO 3 in the power generation cell produced in Example 1, and further the fuel made of Ni and (Ce 0.8 Sm 0.2 ) O 2 of this power generation cell. A conventional solid electrolyte fuel cell 1 was manufactured by laminating a fuel electrode current collector made of a commercially available Ni felt on the electrode side and further laminating a separator on the air electrode current collector and the fuel electrode current collector.
While maintaining the conventional solid electrolyte fuel cell 1 thus obtained at 750 ° C., dry hydrogen gas was allowed to flow as the fuel gas under the same conditions as in Example 1, and air was allowed to flow as the oxidant gas. About the current density: The voltage and electromotive force in 500 mA / cm < 2 > were measured, and the electric power generation performance was evaluated by showing the result in Table 1.
実施例２
実施例１で作製した固体電解質の片面にＮｉと（Ｃｅ0.8Ｓｍ0.2）Ｏ2の体積比が６：４になるように混合したＮｉＯと（Ｃｅ0.8Ｓｍ0.2）Ｏ2の混合粉末を１１００℃で焼付けることにより厚さ：０．０３ｍｍの燃料極を形成し、さらに前記固体電解質の反対側の片面に厚さ：０．０３ｍｍの（Ｓｍ、Ｓｒ）ＣｏＯ3を１０００℃で焼付け、空気極を形成することにより発電セルを作製した。
さらに、実施例１で用意したＡｇコロイドを発電セルの空気極の表面に塗布し乾燥させたのち、得られたＡｇコロイド塗布層を表２に示される温度で焼成することにより表２に示される平均粒径の微細Ａｇ粒子が表２に示される面積率で空気極の表面に均一分散して付着した微細Ａｇ粒子付着空気極を有する微細Ａｇ粒子付着発電セルを作製した。
Example 2
A mixed powder of NiO and (Ce 0.8 Sm 0.2 ) O 2 mixed so that the volume ratio of Ni and (Ce 0.8 Sm 0.2 ) O 2 was 6: 4 on one side of the solid electrolyte prepared in Example 1 was 1100 ° C. A fuel electrode having a thickness of 0.03 mm is formed by baking at a temperature of 0.03 mm, and (Sm, Sr) CoO 3 having a thickness of 0.03 mm is baked at 1000 ° C. on one side opposite to the solid electrolyte. A power generation cell was fabricated by forming
Furthermore, after the Ag colloid prepared in Example 1 is applied to the surface of the air electrode of the power generation cell and dried, the obtained Ag colloid coating layer is baked at the temperature shown in Table 2 and shown in Table 2. A fine Ag particle-attached power generation cell having a fine Ag particle-attached air electrode in which fine Ag particles having an average particle diameter were uniformly dispersed and attached to the surface of the air electrode at an area ratio shown in Table 2 was produced.
さらに、実施例１で用意した市販のＮｉフェルトを先に作製した微細Ａｇ粒子付着発電セルの燃料極側に燃料極集電体として積層し、実施例１で用意した市販の純Ａｇフェルトを微細Ａｇ粒子付着空気極に空気極集電体として積層させ、さらに、実施例１で用意した燃料極側セパレータおよび空気極側セパレータをそれぞれ燃料極集電体および空気極集電体の上に積層させて本発明固体電解質燃料電池１２〜２２、比較固体電解質燃料電池５〜８を作製した。 Further, the commercially available Ni felt prepared in Example 1 was laminated as a fuel electrode current collector on the fuel electrode side of the fine Ag particle-attached power generation cell prepared earlier, and the commercially available pure Ag felt prepared in Example 1 was finely formed. The air electrode current collector is laminated on the Ag particle-attached air electrode, and the fuel electrode side separator and the air electrode side separator prepared in Example 1 are laminated on the fuel electrode current collector and the air electrode current collector, respectively. The present solid electrolyte fuel cells 12 to 22 and comparative solid electrolyte fuel cells 5 to 8 were produced.
このようにして得られた本発明固体電解質燃料電池１２〜２２、比較固体電解質燃料電池５〜８を７５０℃に保持しながら燃料ガスとして乾燥水素ガスを５ｃｃ／ｍｉｎ／ｃｍ２の流量で流し、酸化剤ガスとして空気を流して作動し、本発明固体電解質燃料電池１２〜２２、比較固体電解質燃料電池５〜８について電流密度：５００ｍＡ／ｃｍ２における電圧および起電力を測定し、その結果を表２に示すことにより発電性能を評価した。
While maintaining the solid electrolyte fuel cells 12 to 22 of the present invention and the comparative solid electrolyte fuel cells 5 to 8 thus obtained at 750 ° C., a dry hydrogen gas was allowed to flow as a fuel gas at a flow rate of 5 cc / min / cm 2 , It was operated by flowing air as an oxidant gas, and the voltage and electromotive force at a current density of 500 mA / cm 2 were measured for the solid electrolyte fuel cells 12 to 22 of the present invention and the comparative solid electrolyte fuel cells 5 to 8, and the results are shown. The power generation performance was evaluated by showing in 2.
従来例２
従来例１で作製し用意した純銀フェルトおよび純銀超微粉末燒結層の複合層からなる空気極集電体を実施例２で作製した発電セルにおける（Ｓｍ、Ｓｒ）ＣｏＯ3からなる空気極側に積層した。さらに発電セルのＮｉと（Ｃｅ0.8Ｓｍ0.2）Ｏ2からなる燃料極側に市販のＮｉフェルトからなる燃料極集電体を積層した。
さらにセパレータを前記空気極集電体および燃料極集電体の上に積層させることにより従来固体電解質燃料電池２を作製した。
このようにして得られた従来固体電解質燃料電池２を７５０℃に保持しながら実施例１と同じ条件で燃料ガスとして乾燥水素ガスを流し、酸化剤ガスとして空気を流し、従来固体電解質燃料電池２について電流密度：５００ｍＡ／ｃｍ２における電圧および起電力を測定し、その結果を表２に示すことにより発電性能を評価した。
Conventional example 2
The air electrode current collector composed of a composite layer of pure silver felt and pure silver ultrafine powder sintered layer prepared and prepared in Conventional Example 1 is placed on the air electrode side made of (Sm, Sr) CoO 3 in the power generation cell prepared in Example 2. Laminated. Further, a fuel electrode current collector made of a commercially available Ni felt was laminated on the fuel electrode side made of Ni and (Ce 0.8 Sm 0.2 ) O 2 of the power generation cell.
Further, a conventional solid electrolyte fuel cell 2 was produced by laminating a separator on the air electrode current collector and the fuel electrode current collector.
While maintaining the conventional solid electrolyte fuel cell 2 thus obtained at 750 ° C., dry hydrogen gas was allowed to flow as a fuel gas under the same conditions as in Example 1, air was allowed to flow as an oxidant gas, and the conventional solid electrolyte fuel cell 2 was Current density: The voltage and electromotive force at 500 mA / cm 2 were measured, and the results are shown in Table 2. The power generation performance was evaluated.
表１〜２に示される結果から、微細Ａｇ粒子付着発電セルを組み込んだ本発明固体電解質燃料電池１〜２２は、従来固体電解質形燃料電池１〜２に比べて電流密度：５００ｍＡ／ｃｍ２における電圧および起電力の測定値が優れていることから、本発明固体電解質形燃料電池１〜２２はいずれも従来固体電解質形燃料電池１〜２に比べて優れた発電性能を有することが分かる。しかし、この発明の条件から外れた構成を有する比較固体電解質形燃料電池１〜４は発電性能が十分ではないことが分かる。
From the results shown in Tables 1 and 2, the solid electrolyte fuel cells 1 to 22 of the present invention incorporating the fine Ag particle-attached power generation cell are compared with the conventional solid electrolyte fuel cells 1 and 2 at a current density of 500 mA / cm 2 . Since the measured values of voltage and electromotive force are excellent, it can be seen that all of the solid electrolyte fuel cells 1 to 22 of the present invention have a power generation performance superior to that of the conventional solid electrolyte fuel cells 1 and 2. However, it can be seen that the comparative solid oxide fuel cells 1 to 4 having a configuration deviating from the conditions of the present invention do not have sufficient power generation performance.
Claims (3)
前記発電セルの空気極は、その表面に平均粒径：０．０５〜２μｍの微細Ａｇ粒子が１〜２０面積％均一分散して付着している微細Ａｇ粒子付着空気極であることを特徴とする固体酸化物形燃料電池の発電セル。
General formula: La 1-X Sr X Ga 1-YZ Mg Y Co Z O 3 ( provided that, X = 0.05~0.3, Y = 0~0.29 , Z = 0.01~0.3, An air electrode made of a cobaltite compound is laminated on one side of a solid electrolyte made of an oxide ion conductor represented by Y + Z = 0.025 to 0.3), and the general formula Ce is formed on the other side of the solid electrolyte. 1-m Sm m O 2 , a fuel electrode made of a porous sintered body composed of Sm-doped ceria grains and nickel grains (m is 0 <m ≦ 0.4) is laminated. A power generation cell having the structure
The air electrode of the power generation cell is a fine Ag particle-attached air electrode in which fine Ag particles having an average particle diameter of 0.05 to 2 μm are uniformly dispersed and adhered on the surface thereof. A solid oxide fuel cell power generation cell.
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| JP2010015807A (en) * | 2008-07-03 | 2010-01-21 | Toto Ltd | Solid oxide fuel cell, solid oxide fuel cell unit, and fuel cell module equipped with the same |
| WO2013125457A1 (en) * | 2012-02-22 | 2013-08-29 | 日産自動車株式会社 | Solid oxide fuel cell and method for producing same |
| JP2020149796A (en) * | 2019-03-11 | 2020-09-17 | 住友電気工業株式会社 | Method for manufacturing hydrogen electrode-solid electrolyte layer composite, method for manufacturing cell structure, and method for manufacturing fuel battery |
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