JP2012104308A - Method of producing dense material of electrolyte for solid oxide fuel cell - Google Patents

Method of producing dense material of electrolyte for solid oxide fuel cell Download PDF

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JP2012104308A
JP2012104308A JP2010250535A JP2010250535A JP2012104308A JP 2012104308 A JP2012104308 A JP 2012104308A JP 2010250535 A JP2010250535 A JP 2010250535A JP 2010250535 A JP2010250535 A JP 2010250535A JP 2012104308 A JP2012104308 A JP 2012104308A
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electrolyte
sintering
fuel cell
solid oxide
oxide fuel
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JP5598920B2 (en
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Ray Bi
レイ ビ
Traversa Enrico
トラベルサ エンリコ
Fabbri Emiliana
ファブリ エミリアーナ
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National Institute for Materials Science
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    • 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
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    • Y02E60/50—Fuel cells

Abstract

PROBLEM TO BE SOLVED: To solve such a problem that when the electrolyte of a solid oxide fuel cell operating at intermediate or low temperatures of about 600°C is produced by sintering a raw powder material, an additive element for promoting the sintering is added in order to obtain a dense body because the sinterability of an electrolyte material is low, but this kind of additive inhibits proton conductivity.SOLUTION: The element of a sintering aid which remains in the dense body of sintered electrolyte and inhibits electrical conduction is replaced utilizing solid phase diffusion of other element in an electrode substrate in tight contact therewith. For example, the electrolyte is BaZrO, and the sintering aid of that powder is In. The electrode substrate is NiO doped or BaZrYO. In of the electrolyte is replaced by Y of the electrode to become BaZrYOand shows good proton conductivity.

Description

本発明は、固体酸化物燃料電池用電解質材料において、特に６００℃前後の中低温で伝導率に優れ、化学的に安定である材料を緻密化する新規な製造方法に関する。   The present invention relates to a novel production method for densifying a material that is excellent in conductivity and chemically stable at medium and low temperatures around 600 ° C. in an electrolyte material for a solid oxide fuel cell.

電気エネルギー需要の継続的増加に対して、新しい発電手段の燃料電池が有望視されてきた。その中でも固体酸化物燃料電池の開発は急であり、一部に実用化に至っている。固体酸化物燃料電池に利用される固体酸化物燃料電池材料は金属酸化物固体（セラミックス）であり、８００〜１０００℃で作動させている。これらは高温環境が容易な定置型発電機に利用されているが、自動車等の可動型発電機への利用はまだ実現していない。作動温度が６００℃程度、あるいはそれ以下の中低温になれば、広範囲に利用できる発電機がでる。その経済的、地球環境的、さらに政治的インパクトは大きく、巨大なマーケットが開かれることが期待される。   New power generation fuel cells have been viewed as promising for a continuous increase in electrical energy demand. Among them, the development of solid oxide fuel cells has been rapid, and some have been put into practical use. The solid oxide fuel cell material used for the solid oxide fuel cell is a metal oxide solid (ceramics), which is operated at 800 to 1000 ° C. These are used for stationary generators that are easy to use in high-temperature environments, but have not yet been used for movable generators such as automobiles. If the operating temperature is about 600 ° C. or lower or lower, a generator that can be used in a wide range can be obtained. Its economic, global environmental and political impact is great, and a huge market is expected to be opened.

酸化物固体酸化物燃料電池用電解質では、電子伝導よりプロトン伝導体がイオン電導率に優れているために、有用な材料である。プロトン伝導体の伝導率は、材料そのものイオン電導率と焼結密度および添加元素に大きく左右される。工業材料として使用するためには、伝導率を阻害する添加元素を含まず、緻密化した材料が好ましい。   An electrolyte for an oxide solid oxide fuel cell is a useful material because a proton conductor is superior to electron conduction in ionic conductivity. The conductivity of the proton conductor greatly depends on the ionic conductivity of the material itself, the sintered density, and the additive elements. In order to use as an industrial material, a densified material that does not contain an additive element that hinders conductivity is preferable.

酸化物の固体酸化物燃料電池用電解質材料としては、酸化ジルコニウム（ジルコニア、ＺｒＯ２）があり、高温で酸素イオン伝導体である。これに酸化バリウム（ＢａＯ）や酸化イットリウム（Ｙ２Ｏ３）を固溶させると材料、たとえばＢａＺｒＯ３（ＢＺと記す）、なかでもイットアドープＢａＺｒＯ３（ＢａＺｒｘＹ１−ｘＯ３−δ、ＢＺＹと記す）は優れたプロトン伝導体になり、イオン伝導体よりすぐれている。 As an oxide material for an oxide solid oxide fuel cell, there is zirconium oxide (zirconia, ZrO 2 ), which is an oxygen ion conductor at a high temperature. If barium oxide (BaO) or yttrium oxide (Y 2 O 3 ) is dissolved in this, a material such as BaZrO 3 (referred to as BZ), especially it-doped BaZrO 3 (BaZr x Y 1-x O 3-δ , BZY) ) Is an excellent proton conductor and is superior to the ionic conductor.

ＢＺＹは粉末を焼結して製造するが、焼結性が悪いので緻密体が得られず、十分な電気伝導率を発揮できない。一方、酸化インジウム（Ｉｎ２Ｏ３）や酸化亜鉛（ＺｎＯ）、酸化ニッケル（ＮｉＯ）は焼結助剤として作用し、これらを添加すると焼結を促進し、緻密体が得られる。しかしながら、これらの焼結助剤はプロトン伝導性を阻害し、伝導率を低下させ、その結果、好ましい燃料電池用電解質が得られない。 BZY is produced by sintering powder, but since the sinterability is poor, a dense body cannot be obtained and sufficient electrical conductivity cannot be exhibited. On the other hand, indium oxide (In 2 O 3 ), zinc oxide (ZnO), and nickel oxide (NiO) act as a sintering aid, and when these are added, sintering is promoted and a dense body is obtained. However, these sintering aids inhibit proton conductivity and lower the conductivity, and as a result, a preferable fuel cell electrolyte cannot be obtained.

本発明の課題は、中低温で作動する固体酸化物燃料電池用電解質材料として利用できる材料、たとえばBZYに関して、原料粉末を緻密化させる添加物の利用により緻密体を製造する技術と、それによって電気伝導率が低下しないようにする技術を開発することである。   An object of the present invention is to provide a technique for producing a dense body by using an additive for densifying a raw material powder with respect to a material that can be used as an electrolyte material for a solid oxide fuel cell that operates at medium and low temperatures, for example, BZY, and an electric It is to develop a technology that prevents the conductivity from decreasing.

固体酸化物燃料電池用電解質材料を粉末から焼結するにあたって、焼結性を良くするために焼結助剤として添加物を加え緻密化する。焼結助剤は材料中に残留し、伝導性を阻害する。そこで、焼結後に伝導率を下げなくかつ焼結助剤より高温の揮発性が悪い安定な元素に置換する。このようにして、高いプロトン電気伝率を持つ固体酸化物燃料電池用電解質材料が得られ、本発明に至った。
本発明の一側面によれば、少なくとも固体酸化物燃料電池の電極と電解質からなる部品を粉末からの多結晶体材料を焼結して作成する方法において、前記電解質に含まれている伝導率を阻害する元素を高温で固相拡散することにより他の元素で置換して伝導率を改善する、固体酸化物燃料電池部品製造法が与えられる。
ここで、前記電極及び前記電解質が、前記粉末を原料として、焼結促進剤を添加して、焼結して製造してよい。
また、前記電極と前記電解質が接合しており、高温で仮焼し、固相拡散と元素置換するようにしてよい。
前記電解質がイットリア（Ｙ２Ｏ３）を固溶したＢａＺｒＯ３で組成式がＢａＺｒｘＹ１−ｘＯ３−δであり（ただし、０．１＜ｘ＜０．９９、０．０１＜δ＜０．５）、前記焼結促進剤がＩｎ、Ｇａ、Ｌｉから成る群から選ばれた少なくとも１種の元素を含み、前記少なくとも１種の元素を置換する元素がＹ等の希土類元素であるようにしてよい。 When the electrolyte material for a solid oxide fuel cell is sintered from powder, an additive is added as a sintering aid to improve the sinterability and densify. The sintering aid remains in the material and impedes conductivity. Therefore, it is replaced with a stable element that does not lower the conductivity after sintering and has a lower volatility at a higher temperature than the sintering aid. Thus, an electrolyte material for a solid oxide fuel cell having a high proton electric conductivity was obtained, and the present invention was achieved.
According to one aspect of the present invention, in a method for producing a component comprising at least a solid oxide fuel cell electrode and an electrolyte by sintering a polycrystalline material from powder, the conductivity contained in the electrolyte is determined. A solid oxide fuel cell component manufacturing method is provided in which the interfering element is solid phase diffused at high temperature to replace it with other elements to improve conductivity.
Here, the electrode and the electrolyte may be manufactured by using the powder as a raw material, adding a sintering accelerator, and sintering.
In addition, the electrode and the electrolyte may be joined and calcined at a high temperature to perform solid phase diffusion and element substitution.
The electrolyte is BaZrO 3 in which yttria (Y 2 O 3 ) is dissolved, and the composition formula is BaZr x Y 1-x O 3-δ (where 0.1 <x <0.99, 0.01 <δ <0.5) The sintering promoter contains at least one element selected from the group consisting of In, Ga, and Li, and the element that replaces the at least one element is a rare earth element such as Y. You may do it.

本発明の固体酸化物燃料電池用電解質材料は、中低温で電気伝導が高く、固体酸化物燃料電池の電解質材料に適するものである。これによって、ＣＯ２、ＣＨ４やメタノールなど多様な燃料から、中低温で簡便に電気がえられ、現在世界的に関心のある化石燃料の代替え発電や地球温暖化阻止に貢献する。燃料電池の成功は産業的にも大きな利益になる。 The electrolyte material for a solid oxide fuel cell of the present invention has high electrical conductivity at medium and low temperatures, and is suitable as an electrolyte material for a solid oxide fuel cell. As a result, electricity can be easily obtained from various fuels such as CO 2 , CH 4, and methanol at medium and low temperatures, and it contributes to alternative power generation and global warming prevention of fossil fuels currently of global interest. The success of fuel cells is a big industrial advantage.

本発明の方法を概念的に説明する図。The figure which illustrates the method of this invention notionally. 図の上部は本発明の一実施例で作製した電解質のＸ線回折パターンで、下部はＢＺの標準パターン（ＪＣＰＤＳ Ｃａｒｄ Ｎｏ．０６−０３９９）を示す図。両者は一致して、電解質がＢＺＹであることを示す。右上のＳＥＭ像写真は表面の形状で、緻密な電解質が出来ていることを示す。The upper part of the figure is an X-ray diffraction pattern of the electrolyte prepared in one example of the present invention, and the lower part is a diagram showing a BZ standard pattern (JCPDS Card No. 06-0399). Both agree and indicate that the electrolyte is BZY. The SEM image photograph in the upper right shows that the surface shape is a dense electrolyte. （ａ）は本発明の一実施例で作製した電解質（上部）と電極（下部）の断面のＳＥＭ写真。（ｂ）はＥＤＸによる（ａ）の元素分析結果。Ｂａ、Ｚｒ、ＹとＯは全体に分布し、材料の構成元素である。焼結助剤のＩｎは検出されない。Ｎｉは電極に分布する。(A) is the SEM photograph of the cross section of the electrolyte (upper part) and the electrode (lower part) produced in one Example of this invention. (B) is an elemental analysis result of (a) by EDX. Ba, Zr, Y and O are distributed throughout and are constituent elements of the material. In the sintering aid is not detected. Ni is distributed in the electrodes. Ｉ−Ｖカーブ測定法による本発明の一実施例で作製した電解質のプロトン伝導性の評価を示す図。ここで、直線状の線がＩ−Ｖカーブを、また白抜きのマーカーで表される放物線状の線が電力密度を表している。本発明による電解質が示すピーク電力密度は６００℃で１６９ｍＷｃｍ−２であった。この値は、現在知られている電解質材料の値、２６−１１０ｍＷｃｍ−２、よりはるかに大きい値である。The figure which shows the proton conductivity evaluation of the electrolyte produced in one Example of this invention by the IV curve measuring method. Here, the straight line represents the IV curve, and the parabolic line represented by the white marker represents the power density. The peak power density exhibited by the electrolyte according to the present invention was 169 mWcm −2 at 600 ° C. This value is much larger than the currently known electrolyte material value, 26-110 mWcm −2 . 比較例で作製した焼結助剤Ｉｎを添加しない電解質の焼結材料の表面（ａ）と破壊面（ｂ）を示すＳＥＭ像であり、比較例の電解質は緻密化していないことを示す。It is a SEM image which shows the surface (a) and fracture surface (b) of the sintered material of the electrolyte which does not add sintering auxiliary agent In produced in the comparative example, and shows that the electrolyte of the comparative example is not densified.

中低温で作動する固体酸化物燃料電池用電解質材料ＢＺＹはその粉末を焼結して多結晶体材料に合成され、これをＢＺＹ等の電極基盤に接合して固体酸化物燃料電池にする。ＢＺやＢＺＹの粉末は焼結性が悪く、粉末を仮焼しても緻密体が得られない。そこで、焼結助剤として酸化インジウム（Ｉｎ２Ｏ３）をドープし、インジウムドープＢａＺｒＯ３（ＢＺＩと記す）の粉末を原料とする。Ｉｎ２Ｏ３は一方ではＢＺのプロトン伝導率を低下させる。そこで、Ｉｎ２Ｏ３よりＢＺと親和性がよく高温で安定なＹ２Ｏ３で置換する。すなわち、Ｙ２Ｏ３を含有する電極基盤に接触させて加熱すると、ＹはＢＺＩに進入し、ＩｎがＹに置換される。このようにして、優れたプロトン伝導を持つＢＺＹ固体酸化物燃料電池用電解質材料が得られる。
本発明を適用する材料の最終的な形態は、固体酸化物の電極（陰極）に、本発明の電解質材料が接合され電池を形成する。電解質材料はＢＺにＹ２Ｏ３を固溶した材料が最適であるが、他の希土類酸化物でもよい。電解質はＢＺＩの粉末を焼結して作る。ＩｎはＢＺの焼結助剤として働き、ＢＺＩの緻密な膜が出来る。Ｉｎの代わりにＧａあるいはＬｉでも有効である。電極は組成がＮｉＯを混合したＢＺＹ等が選ばれる。あるいは他の電気伝導性固体でもよい。電極はＮｉＯを含むＢＺＹの粉末を焼結し、板状基盤にする。出発原料の粉末は、均一混合のために有機プレカーサー方法を用いることが好ましい。ＮｉＯは焼結助剤である。このようにして、図１の左端に示すように、電極基盤に電解質の膜ができる。 The solid oxide fuel cell electrolyte material BZY operating at medium and low temperatures is synthesized into a polycrystalline material by sintering the powder, and this is joined to an electrode substrate such as BZY to form a solid oxide fuel cell. BZ and BZY powders have poor sinterability, and a dense body cannot be obtained even if the powder is calcined. Therefore, indium oxide (In 2 O 3 ) is doped as a sintering aid, and indium-doped BaZrO 3 (referred to as BZI) powder is used as a raw material. In 2 O 3 on the other hand decreases the proton conductivity of BZ. Therefore, it is substituted with Y 2 O 3 which has better affinity with BZ than In 2 O 3 and is stable at high temperature. That is, when heated in contact with the electrode substrate containing Y 2 O 3 , Y enters BZI and In is replaced by Y. In this way, an electrolyte material for BZY solid oxide fuel cells having excellent proton conduction can be obtained.
In the final form of the material to which the present invention is applied, the electrolyte material of the present invention is joined to a solid oxide electrode (cathode) to form a battery. The electrolyte material is optimally a material in which Y 2 O 3 is dissolved in BZ, but other rare earth oxides may be used. The electrolyte is made by sintering BZI powder. In acts as a sintering aid for BZ, and a dense BZI film can be formed. Ga or Li is also effective instead of In. For the electrode, BZY mixed with NiO or the like is selected. Alternatively, other electrically conductive solids may be used. The electrode sinters BZY powder containing NiO to form a plate-like substrate. It is preferable to use an organic precursor method for uniform mixing of the starting material powder. NiO is a sintering aid. In this way, as shown at the left end of FIG. 1, an electrolyte membrane is formed on the electrode substrate.

電極基盤と電解質膜の二層構造物を更に仮焼する。このとき、図１の中央に示すように、電極の母材からＹが電解質へ拡散し、Ｉｎと置換する。この置換が起こるのは、ＩｎよりＹがＢＺとの親和性が良く、高温で安定であるからである。十分な仮焼を経ると、図１の右端に示すように、電解質はＢＺＹ（Ｙ−ＢａＺｒＯ３）となり、優れたプロトン伝導体となる。 The two-layer structure of the electrode substrate and the electrolyte membrane is further calcined. At this time, as shown in the center of FIG. 1, Y diffuses from the base material of the electrode into the electrolyte and replaces with In. This substitution occurs because Y has better affinity with BZ than In and is stable at high temperatures. After sufficient calcining, as shown at the right end of FIG. 1, the electrolyte becomes BZY (Y-BaZrO 3 ), and an excellent proton conductor.

以上によって製造した固体酸化物燃料電池部品は、電解質膜がＢＺＹの緻密体で、電解質膜は伝導に有害なＩｎをほとんど含まず、電解質膜が優れたプロトン伝導性をもつ。このようにして得られたイットアドープＢａＺｒＯ３、すなわちＢａＺｒｘＹ１−ｘＯ３−δにおいて、ｘ及びδは夫々以下の範囲の値を取るようにすることで、良好な特性の電解質膜を得ることができる。
０．１＜ｘ＜０．９９
０．０１＜δ＜０．５
なお、本電解質膜中の残留Ｉｎ濃度を１０原子％以下まで低減すれば、プロトン伝導性がかなり改善される。
上述のような方法を用いることにより、厚さが１００μｍ〜１μｍで平均粒径が１０μｍ〜０．１μｍの、これまでになかった薄く且つ緻密な電解質膜を作製することができる。 The solid oxide fuel cell component manufactured as described above has a dense BZY electrolyte membrane, the electrolyte membrane contains almost no In harmful to conduction, and the electrolyte membrane has excellent proton conductivity. In the thus obtained it-doped BaZrO 3 , that is, BaZr x Y 1-x O 3-δ , x and δ take values in the following ranges, respectively, thereby obtaining an electrolyte membrane with good characteristics. be able to.
0.1 <x <0.99
0.01 <δ <0.5
If the residual In concentration in the electrolyte membrane is reduced to 10 atomic% or less, the proton conductivity is considerably improved.
By using the method as described above, an unprecedented thin and dense electrolyte membrane having a thickness of 100 μm to 1 μm and an average particle diameter of 10 μm to 0.1 μm can be produced.

次に、本発明を実施例により、固体酸化物燃料電池用材料の製造と評価結果を具体的に説明する。   Next, the production and evaluation results of the solid oxide fuel cell material will be specifically described by way of examples of the present invention.

化学組成がＢＺＹおよびＢＺＩの粉末を有機プレカーサー法で合成した。電解質用ＢＺＩ粉末ではＢＺ粉末に、Ｉｎ２Ｏ３をＩｎで３０原子％添加した。電極用ＢＺＹ粉末は、Ｙ２Ｏ３にＹを２０原子％加えたＢＺ粉末であるが、さらにＮｉＯも混合した。上記２種の粉末をグリーンシートとして重ね、１４５０℃で仮焼した。
その結果、ＮｉＯ添加ＢＺＹ板状基盤の上に、緻密なＢＺＩ膜が形成された。続けて同温度で１０時間仮焼した。 Powders having chemical compositions of BZY and BZI were synthesized by the organic precursor method. In the BZI powder for electrolyte, In 2 O 3 was added to BZ powder at 30 atomic% as In. The electrode BZY powder is a BZ powder obtained by adding 20 atomic% of Y to Y 2 O 3 , and NiO was also mixed. The two kinds of powders were stacked as green sheets and calcined at 1450 ° C.
As a result, a dense BZI film was formed on the NiO-added BZY plate substrate. Subsequently, it was calcined at the same temperature for 10 hours.

この工程の中で、電極のＢＺＹはＮｉＯ助剤で緻密に焼結した。ＮｉＯは材料内に残留した。電解質のＢＺＩ膜はＩｎ２Ｏ３のために緻密化した。仮焼をそのまま継続することにより、接触しているＢＺＹ電極基盤からＹが電解質膜に拡散してＩｎと置換し、またＩｎは蒸発した。その結果、緻密なＢＺＹ電解質が出来た。焼結と置換の２つの工程は上述のように一連の仮焼工程中で連続的に行われるようにしてもよいし、あるいは焼結と置換をはっきり切り離された別個の肯定としてもよい。なお、電極基盤中にあるＮｉＯは電解質に移動してＩｎを置換することはない。 During this process, the BZY of the electrode was densely sintered with a NiO assistant. NiO remained in the material. The electrolyte BZI film was densified due to In 2 O 3 . By continuing the calcination as it was, Y diffused from the contacting BZY electrode substrate into the electrolyte membrane and replaced with In, and In evaporated. As a result, a dense BZY electrolyte was produced. The two steps of sintering and replacement may be performed continuously in a series of calcination steps as described above, or may be a separate affirmative separation of sintering and replacement. Note that NiO in the electrode substrate does not move to the electrolyte and replace In.

合成した電解質ＢＺＹを評価した。すなわち、結晶構造はＸ線回折パターを測定した。その結果を図２に示す。図２の結果から、合成された電解質の結晶構造はＢＺと一致していることがわかった。なお、ＢＺＹはＢＺと同じ結晶構造を持つ。また、同図に表面のＳＥＭ像も示した。これらから、合成した電解質が緻密体であることが判る。接合した電極基盤と電解質膜の断面をＳＥＭ／ＥＤＳ（走査型電子顕微鏡／エネルギー分散型Ｘ線分析）で分析した。その結果を図３に示す。電解質膜はＢａ、Ｚｒ、ＹとＯからなることと、添加したＩｎがなく、Ｙと置換したことが判り、電解質はＢＺＹと同定された。Ｎｉは電極基盤中に存在し、電解質に拡散していないことも判った。電解質のプロトン伝導性をＩ−Ｖカーブ測定法によって測定し、その結果を図４に示す。温度が６００℃の場合のピーク電力密度は１６９ｍＷｃｍ−２に達し、現在知られている電解質材料の値、２６−１１０ｍＷｃｍ−２、よりはるかに大きい値であった。５００から７００℃の中低温で、優れた電力密度を持ちプロトン伝導性の高い材料が出来ることが判った。 The synthesized electrolyte BZY was evaluated. That is, the X-ray diffraction pattern was measured for the crystal structure. The result is shown in FIG. From the result of FIG. 2, it was found that the crystal structure of the synthesized electrolyte was consistent with BZ. BZY has the same crystal structure as BZ. In addition, an SEM image of the surface is also shown in FIG. From these, it can be seen that the synthesized electrolyte is a dense body. The cross section of the joined electrode substrate and electrolyte membrane was analyzed by SEM / EDS (scanning electron microscope / energy dispersive X-ray analysis). The result is shown in FIG. The electrolyte membrane was made of Ba, Zr, Y and O, and it was found that there was no added In and it was replaced with Y, and the electrolyte was identified as BZY. It was also found that Ni was present in the electrode substrate and did not diffuse into the electrolyte. The proton conductivity of the electrolyte was measured by the IV curve measurement method, and the result is shown in FIG. Peak power density when the temperature is 600 ° C. is reached 169mWcm -2, the value of the electrolyte material currently known, 26-110mWcm -2, was more much larger value. It was found that a material having an excellent power density and high proton conductivity can be obtained at a medium to low temperature of 500 to 700 ° C.

比較例Comparative example

実施例と同じ方法で電極用と電解質用の原料粉末を作った。ただし、電解質にはＩｎを含有していない。これらの粉末を実施例に示した工程によって、電極基盤と電解質膜を作った。図５に示すＳＥＭ像から、比較例で作成した電解質は焼結添加剤のＩｎを含まないため、緻密化していないことがわかった。そのため、この電解質のプロトン伝導性は極めて悪かった。   Raw material powders for electrodes and electrolytes were prepared in the same manner as in the examples. However, the electrolyte does not contain In. Electrode substrates and electrolyte membranes were made from these powders by the process shown in the examples. From the SEM image shown in FIG. 5, it was found that the electrolyte prepared in the comparative example was not densified because it did not contain In as a sintering additive. Therefore, the proton conductivity of this electrolyte was extremely poor.

このように、本発明によれば、焼結助剤を適切に選ぶことによって、緻密な電極基盤と電解質２層材料が合成できた。さらに、有害な添加物の焼結助剤を他元素置換して、優れたプロトン伝導性を発現することが出来る。   Thus, according to the present invention, a dense electrode substrate and an electrolyte two-layer material could be synthesized by appropriately selecting a sintering aid. Furthermore, it is possible to express excellent proton conductivity by substituting the sintering aid for harmful additives with other elements.

本発明によって出来る固体酸化物燃料電池材料は高いプロトン伝導を持つ。固体酸化物燃料電池はアルコールやバイオ燃料を電力に変換するもので、本発明により中低温で作動する材料が得られた。これを工業的に利用すれば、ＣＯ２ガス削減、地球温暖化に貢献し、化石燃料利用依存から脱却することが出来る。 The solid oxide fuel cell material produced by the present invention has high proton conductivity. The solid oxide fuel cell converts alcohol or biofuel into electric power, and a material that operates at medium and low temperatures was obtained by the present invention. If this is used industrially, it contributes to CO 2 gas reduction and global warming, and it is possible to escape from dependence on fossil fuel use.

C. Peng, J. Melnik, J. X. Li, J. L. Luo, A. R. Sanger, K. T. Chuang, J. Power Sources, 2009, 190, 447C. Peng, J. Melnik, J. X. Li, J. L. Luo, A. R. Sanger, K. T. Chuang, J. Power Sources, 2009, 190, 447 Y. M. Guo, Y. Lin, R. Ran, Z. P. Shao, J. Power Sources, 2009, 193, 400Y. M. Guo, Y. Lin, R. Ran, Z. P. Shao, J. Power Sources, 2009, 193, 400 W. P. Sun, L. T. Yan, Z. Shi, Z. W. Zhu, W. Liu, J. Power Sources, 2010, 195, 4727W. P. Sun, L. T. Yan, Z. Shi, Z. W. Zhu, W. Liu, J. Power Sources, 2010, 195, 4727 D. Pergolesi, E. Fabbri, E. Traversa, Electrochem. Commun., 2010, 12, 977D. Pergolesi, E. Fabbri, E. Traversa, Electrochem. Commun., 2010, 12, 977

Claims (4)

少なくとも固体酸化物燃料電池の電極と電解質からなる部品を粉末からの多結晶体材料を焼結して作成する方法において、
前記電解質に含まれている伝導率を阻害する元素を高温で固相拡散することにより他の元素で置換して伝導率を改善する、固体酸化物燃料電池部品製造法。 In a method for producing a component comprising at least a solid oxide fuel cell electrode and an electrolyte by sintering a polycrystalline material from powder,
A method for producing a solid oxide fuel cell component, wherein an element that inhibits conductivity contained in the electrolyte is replaced with another element by solid phase diffusion at high temperature to improve conductivity. 前記電極及び前記電解質が、前記粉末を原料として、焼結促進剤を添加して、焼結して製造する、請求項１の製造方法。 The manufacturing method according to claim 1, wherein the electrode and the electrolyte are manufactured by adding a sintering accelerator and sintering the powder as a raw material. 前記電極と前記電解質が接合しており、高温で仮焼し、固相拡散と元素置換する、請求項１の製造方法。 The manufacturing method according to claim 1, wherein the electrode and the electrolyte are joined, calcined at a high temperature, solid phase diffusion and element substitution. 前記電解質がイットリア（Ｙ２Ｏ３）を固溶したＢａＺｒＯ３で組成式がＢａＺｒｘＹ１−ｘＯ３−δであり（ただし、０．１＜ｘ＜０．９９、０．０１＜δ＜０．５）、前記焼結促進剤がＩｎ、Ｇａ、Ｌｉから成る群から選ばれた少なくとも１種の元素を含み、前記少なくとも１種の元素を置換する元素がＹ等の希土類元素である、請求項１の製造方法。
The electrolyte is BaZrO 3 in which yttria (Y 2 O 3 ) is dissolved, and the composition formula is BaZr x Y 1-x O 3-δ (where 0.1 <x <0.99, 0.01 <δ <0.5) The sintering promoter contains at least one element selected from the group consisting of In, Ga, and Li, and the element that replaces the at least one element is a rare earth element such as Y. The manufacturing method of Claim 1.
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