JPH0758615B2 - Solid electrolyte fuel cell - Google Patents
Solid electrolyte fuel cellInfo
- Publication number
- JPH0758615B2 JPH0758615B2 JP1270794A JP27079489A JPH0758615B2 JP H0758615 B2 JPH0758615 B2 JP H0758615B2 JP 1270794 A JP1270794 A JP 1270794A JP 27079489 A JP27079489 A JP 27079489A JP H0758615 B2 JPH0758615 B2 JP H0758615B2
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- electrode
- fuel
- fuel electrode
- air electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000446 fuel Substances 0.000 title claims description 53
- 239000007784 solid electrolyte Substances 0.000 title claims description 22
- 239000012212 insulator Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 7
- 230000002093 peripheral effect Effects 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000002737 fuel gas Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- -1 oxygen ions Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910017563 LaCrO Inorganic materials 0.000 description 2
- 229910018279 LaSrMnO Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011195 cermet Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- 230000035699 permeability Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Fuel Cell (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、固体電解質燃料電池に関し、特に安価で高性
能な固体電解質燃料電池スタックに関する。TECHNICAL FIELD The present invention relates to a solid electrolyte fuel cell, and more particularly to an inexpensive and high performance solid electrolyte fuel cell stack.
空気極、燃料極および固体電解質を有する固体電解質燃
料電池（以下SOFCと略記）において、電解質としてZrO2
-Y2O3（以下YSZと略記）を使用し、1000℃程度の温度に
保持すると、電気化学反応が起こる。1000℃は、YSZが
実用的と考えられている導電率（〜10Ω-1cm-1）を示す
温度である。In a solid electrolyte fuel cell (hereinafter abbreviated as SOFC) having an air electrode, a fuel electrode and a solid electrolyte, ZrO 2 is used as an electrolyte.
When -Y 2 O 3 (hereinafter abbreviated as YSZ) is used and kept at a temperature of about 1000 ° C, an electrochemical reaction occurs. 1000 ° C is the temperature at which YSZ exhibits a conductivity (~ 10 Ω -1 cm -1 ) that is considered practical.
電気化学反応は以下のようにして起こる。空気極におい
て酸素がイオン化されて酸素イオンが発生し、この酸素
イオンが電解質内を燃料極に向かって移動し、燃料極の
界面において酸素イオンと水素とが反応して水を生成す
ると同時に電子が発生する。空気極と燃料極との間に外
部負荷を接続すると、これら２つの電極および外部負荷
で形成される回路に電流が流れ、電力を取りだすことが
できる。このときの起電力（Ｅ）は次式から得られる。The electrochemical reaction occurs as follows. Oxygen is ionized at the air electrode and oxygen ions are generated.The oxygen ions move in the electrolyte toward the fuel electrode, and at the interface of the fuel electrode, oxygen ions react with hydrogen to generate water, and at the same time electrons are generated. Occur. When an external load is connected between the air electrode and the fuel electrode, an electric current flows through the circuit formed by these two electrodes and the external load, and electric power can be taken out. The electromotive force (E) at this time is obtained from the following equation.
Ｅ＝（RT/4F）1n（PO1／PO2） （１） ここで、Ｒ＝ガス定数、Ｔ＝温度（Ｋ）、Ｆ＝ファラデ
ー定数、PO1,PO2＝それぞれ空気極および燃料極におけ
る酸素分圧である。E = (RT / 4F) 1n (P O1 / P O2 ) (1) where R = gas constant, T = temperature (K), F = Faraday constant, P O1 , P O2 = air electrode and fuel electrode, respectively Is the oxygen partial pressure at.
燃料極では次の反応が発生している。The following reactions occur at the fuel electrode.
O2+2H2＝2H2O 燃料極におけるそれぞれの分圧を、PO2,PH2,PH2O、平衡
定数をＫとすると、 Ｋ＝PH2O/PH2(PO2)1/2となり、この式からPO2を導いて
（１）式に代入すると、 Ｅ＝RT/2FlnK＋（RT/2F）1n（PH2(PO1)1/2/PH2O）とな
り、RT/2FlnK＝EOとおくと次式が得られる。O 2 + 2H 2 = 2H 2 O Letting each partial pressure at the fuel electrode be P O2 , P H2 , P H2O and the equilibrium constant K, K = P H2O / P H2 (P O2 ) 1/2 , Substituting P O2 from this formula and substituting it in formula (1) gives E = RT / 2FlnK + (RT / 2F) 1n (P H2 (P O1 ) 1/2 / P H2O ), and RT / 2FlnK = E O The following equation is obtained by putting it.
Ｅ＝EO＋（RT/2F）1n（PH2(PO1)1/2/PH2O） （２） ここで、EOは平衡状態での標準起電力（1000℃において
0.92V）である。E = E O ＋ (RT / 2F) 1n (P H2 (P O1 ) 1/2 / P H2O ) (2) where E O is the standard electromotive force in equilibrium (at 1000 ° C
0.92V).
（２）式から、燃料電池の起電力は空気極に接する酸素
の分圧（PO1）および燃料極に接する水の分圧（PH2O）
にほぼ依存していることがわかる。From equation (2), the electromotive force of the fuel cell is the partial pressure of oxygen in contact with the air electrode (P O1 ) and the partial pressure of water in contact with the fuel electrode (P H2O ).
It turns out that it is almost dependent on.
以上説明したような原理に基づき、第２図および第３図
に示す構造をもつSOFCが製作されている。An SOFC having the structure shown in FIGS. 2 and 3 is manufactured based on the principle described above.
第２図に示すSOFCは円筒状多孔質セラミック基体管１に
燃料極２、電解質３、空気極４およびインターコネクタ
５それぞれの薄膜（70〜150μｍ）を溶射技術により順
次積層して、SOFCの単電池（単セル）を形成すると同時
に単電池（単セル）を直列接続により集積し、SOFCスタ
ックを形成している。The SOFC shown in FIG. 2 has a structure in which a thin film (70 to 150 μm) of each of a fuel electrode 2, an electrolyte 3, an air electrode 4 and an interconnector 5 is sequentially laminated on a cylindrical porous ceramic substrate tube 1 by a thermal spraying technique to form a single SOFC. At the same time as forming the battery (single cell), the single cells (single cell) are integrated by series connection to form an SOFC stack.
このSOFCは通常、円筒内部に燃料ガスである水素を流
し、外周に空気を流して電気化学反応を起こすことによ
り発電を行なう。このとき、電流は円筒の軸方向に流れ
る。このSOFC構造は、基体管１としては多孔質のアルミ
ナチューブを使用し、基体管１上に燃料極２として（Ni
＋YSZ）サーメットを、電解質３としてYSZを溶射被覆す
る。さらに、空気極４およびインターコネクタ５とし
て、熱的に比較的不安定な構造を持つペロブスカイト型
酸化物であるLaCoO3あるいはLaCrO3を同様に積層してい
る。In this SOFC, hydrogen, which is a fuel gas, is caused to flow inside the cylinder, and air is caused to flow at the outer periphery to cause an electrochemical reaction to generate electricity. At this time, the current flows in the axial direction of the cylinder. In this SOFC structure, a porous alumina tube is used as the base tube 1, and a fuel electrode 2 (Ni
+ YSZ) Cermet is spray coated with YSZ as electrolyte 3. Further, as the air electrode 4 and the interconnector 5, LaCoO 3 or LaCrO 3 which is a perovskite type oxide having a thermally unstable structure is similarly laminated.
隣接層との熱膨張係数の不整合による剥離を抑制するた
め、各電極の膜厚は150μｍ以下に設定されている。こ
のため、スタックの軸方向に沿って電気抵抗が大きくな
り、また、各層に内蔵される気孔を通して燃料ガスの漏
洩が顕著であり、このため燃料利用率が極めて低くな
る。The thickness of each electrode is set to 150 μm or less in order to suppress the peeling due to the mismatch of the thermal expansion coefficient with the adjacent layer. For this reason, the electric resistance increases along the axial direction of the stack, and the leakage of the fuel gas is remarkable through the pores built in each layer, resulting in a very low fuel utilization rate.
第３図に示すSOFCは基本的には第２図に示した構造と同
様であり、円筒状の多孔質セラミック基体管６に空気極
7,電解質8,燃料極９およびインターコネクタ10の薄膜
（50〜700μｍ）を化学蒸着（CVD）法または電気化学蒸
着（EVD）法により順次積層し、単セルがスタックを形
成するように構造を簡略化している。このSOFCでは円筒
内部に予熱した空気を流し、外周に燃料ガスを流して電
気化学反応を起こすことにより発電を行なう。このと
き、電流は円筒の外周方向に流れる。The SOFC shown in FIG. 3 is basically the same as the structure shown in FIG. 2, and the SOFC shown in FIG.
7, Electrolyte 8, Fuel electrode 9 and Thin film (50-700μm) of interconnector 10 are sequentially laminated by chemical vapor deposition (CVD) method or electrochemical vapor deposition (EVD) method to form a structure so that a single cell forms a stack. It's simplified. In this SOFC, preheated air is made to flow inside the cylinder, and fuel gas is made to flow at the outer periphery to cause an electrochemical reaction to generate electricity. At this time, the current flows in the outer peripheral direction of the cylinder.
この例では電流を外周方向に流す単電池構造とすること
によりセルの電気抵抗を低下させることを特徴としてお
り、さらに電極やインターコネクタ部から漏洩する燃料
ガスを確実に密封する考慮が払われている。This example is characterized by reducing the electric resistance of the cell by adopting a single cell structure in which a current flows in the outer peripheral direction, and further consideration is given to surely sealing the fuel gas leaking from the electrodes and the interconnector part. There is.
すなわち、基体管６の作製には多孔質のジルコニア（Zr
O2−CaO）が使用される。基体管６の上に空気極７とし
てLaSrMnO3をスラリー焼結し、電解質８としてYSZを積
層する。さらに電解質８の上に、EVD法またはCVD法によ
りインターコネクタ10としてLaMgCrO3を無気孔の緻密膜
として積層する。電解質８であるYSZ膜上に燃料極９と
して積層される（Ni＋YSZ）サーメットには、空気極７
として積層されるLaSrMnO3と同様にスラリー焼結法が採
用されている。That is, in order to manufacture the base tube 6, porous zirconia (Zr
O 2 -CaO) is used. LaSrMnO 3 as the air electrode 7 is slurry-sintered on the base tube 6 and YSZ is laminated as the electrolyte 8. Furthermore, LaMgCrO 3 is laminated as an interconnector 10 on the electrolyte 8 by an EVD method or a CVD method as a non-porous dense film. For the cermet (Ni + YSZ) laminated as the fuel electrode 9 on the YSZ film that is the electrolyte 8, the air electrode 7
The slurry sintering method is adopted as in the case of LaSrMnO 3 laminated as.
SOFCの製作技術は、燃料極および空気極における燃料ガ
スの透過性と、電解質およびインターコネクタにおける
気密性という相反する特性を持った薄膜を製作すること
に重要な鍵がある。The fabrication technology of SOFC has an important key to produce a thin film having the contradictory properties of fuel gas permeability at the fuel electrode and air electrode and airtightness at the electrolyte and interconnector.
上述したように、燃料ガス透過性薄膜の製作技術として
スラリー焼結法や溶射技術が応用され、気密性薄膜の製
作法としてCVD法やEVD法などによる蒸着技術が応用され
ている。As described above, the slurry sintering method and the thermal spraying technology are applied as the manufacturing technology of the fuel gas permeable thin film, and the vapor deposition technology such as the CVD method and the EVD method is applied as the manufacturing method of the airtight thin film.
しかし、スラリー焼結法は均質膜と厚膜の実現が困難で
あり、溶射技術は作業温度が高くかつ局部加熱により施
工されるので、内部応力や歪の発生を伴いやすく、スタ
ックの寸法精度をそれほど高くすることはできない。However, it is difficult to realize a homogeneous film and a thick film in the slurry sintering method, and since the spraying technology has a high working temperature and is applied by local heating, internal stress and strain are likely to occur, and stack dimensional accuracy is improved. It cannot be so high.
一方、CVD法およびEVD法などはその成膜プロセスから製
造コストが高くなるので、量産には適さない。これ等の
成膜技術は何れも基体管上に、厚さ700μｍ以下の薄膜
層として積層され、成膜層が独自にスタックの機械強度
を分担したり組み立て精度を出すことはできない。さら
に、この製作技術では何れも空気極および燃料極の通電
断面積を広く取ることができず、このためセル内部抵抗
の発電出力への影響が大きい等の問題点がある。On the other hand, the CVD method and the EVD method are not suitable for mass production because the manufacturing cost increases due to the film forming process. All of these film forming techniques are laminated as a thin film layer having a thickness of 700 μm or less on the substrate tube, and the film forming layer cannot independently contribute to the mechanical strength of the stack and cannot provide the assembly accuracy. Further, in this manufacturing technique, the energization cross-sectional areas of the air electrode and the fuel electrode cannot be made wide, and therefore, there is a problem that the internal resistance of the cell has a great influence on the power generation output.
本発明は上述の問題点を補い、あるいはそれ等の問題点
を解決するためになされたものであり、電解質，空気
極，燃料極およびインターコネクタを単独あるいは複合
部材として製作し、それ等各部材間の結合は有効な接合
技術を応用して行なうと共に、動作時の熱膨張差を利用
して部材間の接触強化を行なった構成により安価で高性
能なSOFCスタックを提供することにある。The present invention has been made in order to supplement the above-mentioned problems or solve the problems. An electrolyte, an air electrode, a fuel electrode and an interconnector are manufactured as a single member or a composite member, and each member thereof is manufactured. It is to provide an inexpensive and high-performance SOFC stack by applying an effective joining technique and strengthening the contact between members by utilizing the difference in thermal expansion during operation.
このような目的を達成するために、本発明は、円筒の内
側から外周方向に積層された燃料極，固体電解質，空気
極を有する単電池をインターコネクタで集積した円筒型
の固体電解質燃料電池において、前記空気極が前記燃料
極および前記固体電解質を形成する物質の熱膨張係数よ
りも小さい熱膨張係数の物質で形成され、前記インター
コネクタが前記燃料極，前記固体電解質および前記空気
極に隣接して前記燃料極および前記固体電解質よりも熱
膨張係数の小さい絶縁体内側に形成された導体であるこ
とを特徴とする。In order to achieve such an object, the present invention provides a cylindrical solid electrolyte fuel cell in which unit cells having a fuel electrode, a solid electrolyte, and an air electrode that are stacked from the inside to the outside of a cylinder are integrated with an interconnector. The air electrode is formed of a material having a coefficient of thermal expansion smaller than that of a material forming the fuel electrode and the solid electrolyte, and the interconnector is adjacent to the fuel electrode, the solid electrolyte and the air electrode. And a conductor formed inside an insulator having a smaller thermal expansion coefficient than the fuel electrode and the solid electrolyte.
［作用］ 本発明は円筒状固体電解質燃料電池の単電池構成におい
て、燃料極および空気極を各々独立して多孔質焼成品
（厚さｔ＝１〜2mm）として製作し、それ等に従来の基
体管としてのセル構造強度保持機能と通電断面積の拡大
による低インピーダンス化を合せて付与したものであ
る。これにより積層構成および製作工程の単純化と電池
の発電性能並びに耐久性能が向上し、低コストの固体電
解質燃料電池の製造が可能となる。また、外周方向に僅
かずつ熱膨張係数を低くしてゆく積層構成により、動作
温度での熱膨張歪を拘束し各層間および電極インターコ
ネクタ間の接触が強化され、良好な気密性や電気的損失
の低いスタック構成を実現する。[Operation] In the present invention, in the unit cell structure of the cylindrical solid oxide fuel cell, the fuel electrode and the air electrode are independently manufactured as porous fired products (thickness t = 1 to 2 mm), and the conventional products are used for them. The function of maintaining the strength of the cell structure of the base tube and the reduction of impedance by enlarging the cross-sectional area of the current are added together. As a result, the laminated structure and the manufacturing process are simplified, the power generation performance and the durability performance of the cell are improved, and it becomes possible to manufacture a low cost solid electrolyte fuel cell. In addition, the laminated structure that gradually lowers the thermal expansion coefficient in the outer peripheral direction restrains the thermal expansion strain at the operating temperature and strengthens the contact between each layer and the electrode interconnector, resulting in good airtightness and electrical loss. Achieve a low stack configuration.
本発明は円筒状固体電解質燃料電池において、最内層が
中空円筒状の燃料極（多孔質焼成品、厚さｔ＝１〜2m
m）上に緻密質固体電解質の蒸着薄膜（数μｍ〜数十μ
ｍ）または緻密質焼成品（ｔ＝１〜2mm）を被覆し、さ
らにその上層に空気極（多孔質焼成品、ｔ＝１〜2mm）
を接合し、電解質、空気極および燃料極外周に気密と電
気絶縁を兼ねたインターコネクタを内蔵する絶縁体を具
備した固体電解質燃料電池である。この構成において、
燃料極および電解質の熱膨張係数は空気極のそれよりも
等しいか若干大きい材料を選定し、さらに、絶縁体は燃
料極および電解質より熱膨張係数が僅かに小さな材料を
選定する必要がある。また、インターコネクタの熱膨張
係数は絶縁体とほぼ同様の値を持つように材料を選定す
る。INDUSTRIAL APPLICABILITY The present invention relates to a cylindrical solid electrolyte fuel cell, in which the innermost layer is a hollow cylindrical fuel electrode (porous fired product, thickness t = 1 to 2 m).
m) Deposition thin film of dense solid electrolyte (several μm to several tens μ)
m) or a dense fired product (t = 1 to 2 mm), and an air electrode (porous fired product, t = 1 to 2 mm) on the upper layer.
And a solid electrolyte fuel cell having an insulator, which is joined to each other, and has an interconnector having airtightness and electrical insulation built in around the electrolyte, the air electrode and the fuel electrode. In this configuration,
It is necessary to select a material in which the thermal expansion coefficient of the fuel electrode and the electrolyte is equal to or slightly larger than that of the air electrode, and further, to select the insulator, a material whose thermal expansion coefficient is slightly lower than that of the fuel electrode and the electrolyte. In addition, the material is selected so that the coefficient of thermal expansion of the interconnector has almost the same value as the insulator.
以下に、第１図を参照して本発明の一実施例を詳細に説
明する。第１図において、11は燃料極であり、金属（N
i）と酸化物（YSZ）との混合物（熱膨張係数＝12×10-6
／℃）を焼成して多孔質焼成品とし、その厚みを2mmと
している。燃料極11はSOFCの最内層を構成するものであ
り、単電池の剛性の大部分をこの層が分担する。An embodiment of the present invention will be described in detail below with reference to FIG. In FIG. 1, 11 is a fuel electrode, which is a metal (N
i) and oxide (YSZ) mixture (coefficient of thermal expansion = 12 × 10 -6
/ ° C) to obtain a porous fired product with a thickness of 2 mm. The fuel electrode 11 constitutes the innermost layer of the SOFC, and this layer shares most of the rigidity of the unit cell.
YSZ（熱膨張係数＝10.5×10-6／℃）からなる電解質12
は水素漏洩防止の観点より、薄膜（厚さ10μｍ）を化学
蒸着法により、または緻密質焼成品（厚さ1mm）を耐還
元性導電接着剤により接合する。耐還元性導電接着剤と
しては、カーボンを基材としたカーボンセメントなどが
ある。Electrolyte composed of YSZ (coefficient of thermal expansion = 10.5 x 10 -6 / ° C) 12
In order to prevent hydrogen leakage, a thin film (10 μm thick) is bonded by chemical vapor deposition, or a dense fired product (1 mm thick) is bonded by a reduction resistant conductive adhesive. Examples of reduction-resistant conductive adhesives include carbon cement based on carbon.
混合導電性のLa0.5Ca0.5MnO3（熱膨張係数＝10×10-6／
℃）空気極13は燃料極11と同様の製法および厚みで製造
し、熱膨張を中心軸方向に作用させるために、円筒軸方
向に沿って２〜４分割し、それ等を耐酸化性導電接着剤
によりYSZ電解質12に接合する。耐酸化性導電接着剤と
しては、ZrO2,LaCrO3,CeO2あるいはPt等を単独あるいは
複合化し、有機または無機バインダーで固定化するもの
であり、例えば白金ペースト等がある。Mixed conductivity La 0.5 Ca 0.5 MnO 3 (coefficient of thermal expansion = 10 × 10 -6 /
(° C) The air electrode 13 is manufactured by the same manufacturing method and thickness as the fuel electrode 11, and is divided into 2 to 4 along the axial direction of the cylinder in order to cause thermal expansion in the central axial direction. It is bonded to the YSZ electrolyte 12 with an adhesive. As the oxidation resistant conductive adhesive, ZrO 2 , LaCrO 3 , CeO 2 or Pt or the like is used alone or in combination, and is fixed with an organic or inorganic binder, such as platinum paste.
Al2O3（熱膨張係数＝8.0×10-6／℃）絶縁体14および15
は、単電池間の電気的接続および燃料ガス（水素）の気
密保持機能が必要であるため、緻密質焼成品を使用して
メタライズ接合により両者を一体化する。このメタライ
ズ層はインターコネクタ16として作用する。Al 2 O 3 (coefficient of thermal expansion = 8.0 × 10 -6 / ℃) Insulators 14 and 15
Requires a function of electrical connection between the unit cells and a function of maintaining the airtightness of the fuel gas (hydrogen). Therefore, a dense fired product is used to integrate the two by metallization joining. This metallization layer acts as an interconnector 16.
メタライズ層16と空気極13との接合部17およびメタライ
ズ層16と燃料極11との接合部18は、それぞれ酸化性雰囲
気および還元性雰囲気に耐え得る導電性接着剤や貴金属
箔を挿入し、あるいは発泡性金属からなるスペーサ19等
により電気的接合を確実に行ない得る。A joint 17 between the metallized layer 16 and the air electrode 13 and a joint 18 between the metallized layer 16 and the fuel electrode 11 are respectively inserted with a conductive adhesive or a noble metal foil capable of withstanding an oxidizing atmosphere and a reducing atmosphere, or Electrical connection can be surely performed by the spacer 19 made of foam metal.
単電池の複数個を組み合わせてスタックを形成する際
に、その寸法精度や偏心誤差は燃料通路にSi3N4（熱膨
張係数＝4.0×10-6／℃）等のような熱膨張の小さい中
子管20を挿入して組み立てを行ない、熱処理後、中子管
20を摘出する。中子管20について説明する。SOFC構成部
材を接合して組み立てる際に、それぞれのセンターと軸
方向の直線性および寸法精度を正確に出す必要があり、
この補助治具として中子管20を用いる。普通、耐熱性接
着剤は高温での熱処理が要求されるので、耐熱性中子
（Si3N4等）を使用する必要がある。中子管20は接着剤
の熱処理後摘出され、再使用される。When combining a plurality of unit cells to form a stack, the dimensional accuracy and eccentricity error are small in thermal expansion such as Si 3 N 4 (coefficient of thermal expansion = 4.0 x 10 -6 / ° C) in the fuel passage. Insert the core tube 20 to assemble, heat-treat, then insert the core tube
Remove 20. The core tube 20 will be described. When joining and assembling SOFC components, it is necessary to accurately show the linearity and dimensional accuracy of each center and axial direction,
The core tube 20 is used as this auxiliary jig. Usually, heat-resistant adhesives require heat treatment at high temperatures, so it is necessary to use heat-resistant cores (Si 3 N 4, etc.). The core tube 20 is extracted after heat treatment of the adhesive and is reused.
絶縁体14の内径は燃料極11の内径より１〜2mm小さく
し、絶縁体14に内接するように中子管20の外径を設定す
る。また、絶縁体15の燃料通路への突起部は燃料ガスの
流れ場において乱流の形成を促進し、燃料利用率の向上
に寄与する。The inner diameter of the insulator 14 is made 1 to 2 mm smaller than the inner diameter of the fuel electrode 11, and the outer diameter of the core tube 20 is set so as to be inscribed in the insulator 14. Further, the protrusion of the insulator 15 to the fuel passage promotes the formation of turbulence in the flow field of the fuel gas and contributes to the improvement of the fuel utilization rate.
以上説明したように本発明によれば、以下の効果を得る
ことができる。As described above, according to the present invention, the following effects can be obtained.
（１）円筒型SOFCの構成上、基体管を省略し電極および
電解質を個別に製作して組み立てる構成とすることによ
り、電極断面積増加による軸方向電気抵抗の減少による
電気出力密度の増大並びに積層構造の単純化による製作
コストの低減を実現することができる。(1) In the structure of the cylindrical SOFC, by omitting the substrate tube and manufacturing and assembling the electrode and the electrolyte individually, the electric power density is increased and the electric power density is increased due to the decrease of the axial electric resistance due to the increase of the electrode cross-sectional area and the lamination. It is possible to reduce the manufacturing cost by simplifying the structure.
（２）燃料極，電解質，空気極および絶縁体等の熱膨張
差を積極的に利用することにより、SOFCの円筒軸方向に
圧縮応力を作用せしめ、耐ピーリング構造、耐クラック
構造および耐スポーリング構造を実現することができ
る。また、圧縮応力による各層の歪は単電池間の気密性
および電気的接続を確実なものにする。(2) By positively utilizing the difference in thermal expansion between the fuel electrode, electrolyte, air electrode, insulator, etc., compressive stress acts in the axial direction of the SOFC cylinder, so that it is resistant to peeling, cracking and spalling. The structure can be realized. Further, the strain of each layer due to the compressive stress ensures airtightness and electrical connection between the unit cells.
（３）十分な強度と高い寸法精度とを持つ電極およびイ
ンターコネクタを製作することができるので、単電池性
能が向上し、スタック化およびモジュール化が容易とな
る。(3) Since electrodes and interconnectors having sufficient strength and high dimensional accuracy can be manufactured, cell performance is improved and stacking and modularization are facilitated.
（４）SOFC構成要素の品質管理が容易であり、スタック
製作時の信頼性が向上する。(4) It is easy to control the quality of SOFC components and improve the reliability during stack fabrication.
第１図は本発明の一実施例に係る固体電解質燃料電池ス
タックの縦方向断面図、 第２図および第３図は従来の固体電解質燃料電池の縦方
向断面図である。 11……燃料極、12……電解質、13……空気極、14,15…
…絶縁体、16……インターコネクタ、17,18……接合
体、19……スペーサ、20……中子管。FIG. 1 is a vertical sectional view of a solid electrolyte fuel cell stack according to an embodiment of the present invention, and FIGS. 2 and 3 are vertical sectional views of a conventional solid electrolyte fuel cell stack. 11 …… Fuel electrode, 12 …… Electrolyte, 13 …… Air electrode, 14,15…
… Insulator, 16 …… Interconnector, 17,18 …… Joined body, 19 …… Spacer, 20 …… Core tube.
Claims (1)
極，固体電解質，空気極を有する単電池をインターコネ
クタで集積した円筒型の固体電解質燃料電池において、
前記空気極が前記燃料極および前記固体電解質を形成す
る物質の熱膨張係数よりも小さい熱膨張係数の物質で形
成され、前記インターコネクタが前記燃料極，前記固体
電解質および前記空気極に隣接して前記燃料極および前
記固体電解質よりも熱膨張係数の小さい絶縁体内側に形
成された導体であることを特徴とする固体電解質燃料電
池。1. A cylindrical solid electrolyte fuel cell in which unit cells having a fuel electrode, a solid electrolyte, and an air electrode, which are laminated from the inside of a cylinder to the outer peripheral direction, are integrated by an interconnector,
The air electrode is formed of a material having a coefficient of thermal expansion smaller than that of a material forming the fuel electrode and the solid electrolyte, and the interconnector is adjacent to the fuel electrode, the solid electrolyte and the air electrode. A solid electrolyte fuel cell, which is a conductor formed inside an insulator having a thermal expansion coefficient smaller than that of the fuel electrode and the solid electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1270794A JPH0758615B2 (en) | 1989-10-18 | 1989-10-18 | Solid electrolyte fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1270794A JPH0758615B2 (en) | 1989-10-18 | 1989-10-18 | Solid electrolyte fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03133064A JPH03133064A (en) | 1991-06-06 |
| JPH0758615B2 true JPH0758615B2 (en) | 1995-06-21 |
Family
ID=17491099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1270794A Expired - Lifetime JPH0758615B2 (en) | 1989-10-18 | 1989-10-18 | Solid electrolyte fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0758615B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4883968B2 (en) * | 2005-09-27 | 2012-02-22 | 京セラ株式会社 | Fuel cell manufacturing method |
| JP5241663B2 (en) * | 2009-09-14 | 2013-07-17 | 京セラ株式会社 | Solid electrolyte fuel cell stack, bundle and fuel cell |
| JP4872027B1 (en) * | 2010-11-01 | 2012-02-08 | 日本碍子株式会社 | Solid oxide fuel cell |
| JP6277808B2 (en) * | 2014-03-24 | 2018-02-14 | アイシン精機株式会社 | Solid oxide fuel cell stack, solid oxide fuel cell module, and solid oxide fuel cell system |
-
1989
- 1989-10-18 JP JP1270794A patent/JPH0758615B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03133064A (en) | 1991-06-06 |
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