TW201332206A - Fuel cell electrolyte, solid oxide fuel cell and manufacturing method thereof - Google Patents
Fuel cell electrolyte, solid oxide fuel cell and manufacturing method thereof Download PDFInfo
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
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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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- 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
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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
- 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
Abstract
Description
本發明係有關固態氧化物燃料電池(SOFC：Solid Oxide Fuel Cell)之製造技術，特別是有關氣密性優良之燃料電池用電解質、及具備該種電解質之固態氧化物燃料電池、以及該燃料電池之製造方法。 The present invention relates to a manufacturing technology of a solid oxide fuel cell (SOFC), particularly an electrolyte for a fuel cell excellent in airtightness, and a solid oxide fuel cell including the electrolyte, and the fuel cell Manufacturing method.
固態氧化物燃料電池中，係使用具備氧離子傳導性之氧化釔安定氧化鋯(Yttria Stabilized Zirconia,YSZ)等固體氧化物所構成之電解質，構造為其兩側配置具有氣體透過性之電極，以近1000℃的高溫動作。 In the solid oxide fuel cell, an electrolyte composed of a solid oxide such as Yttria Stabilized Zirconia (YSZ) having oxygen ion conductivity is used, and an electrode having gas permeability is disposed on both sides thereof. High temperature operation at 1000 °C.
在製作這種固態氧化物燃料電池的電解質時，以網版印刷法較簡便，為製造方法之主流。但該方法需要1200℃以上之熱處理，必須將金屬支撐型電池的支撐基板做成耐熱合金，無法以廉價材料代替，故無法降低材料成本。 In the production of the electrolyte of such a solid oxide fuel cell, the screen printing method is relatively simple and is the mainstream of the manufacturing method. However, this method requires heat treatment at 1200 ° C or higher, and the support substrate of the metal-supported battery must be made into a heat-resistant alloy, and cannot be replaced with an inexpensive material, so that the material cost cannot be reduced.
另一方面，按照物理蒸鍍法(PLD法，濺鍍法等)，在1000℃以下、常溫亦可成膜，但成膜基板並非平坦且緻密的情形下或是常溫成膜的情形下，會變成間隙多的柱狀結晶構造，無法確保氣密性，對電解質而言是致命 的缺點。 On the other hand, according to the physical vapor deposition method (PLD method, sputtering method, etc.), the film can be formed at a temperature of 1000 ° C or lower at normal temperature, but in the case where the film formation substrate is not flat and dense, or is formed at room temperature, It will become a columnar crystal structure with a large gap, which cannot ensure airtightness and is fatal to electrolytes. Shortcomings.
因此，以往均在柱狀結晶間隙填入膨脹材料，例如專利文獻1中提出一種方法，是在柱狀結晶上部形成會氧化膨脹之層，藉由對其進行氧化處理而提升氣密性。 For this reason, in the prior art, the expanded material is filled in the columnar crystal gap. For example, Patent Document 1 proposes a method in which a layer which oxidizes and swells is formed on the upper portion of the columnar crystal, and the airtightness is improved by oxidizing the layer.
然而，按上述專利文獻1所記載之方法，在氧化膨脹時會於電解質膜產生強烈應力，故會發生裂痕或剝離、或是氧化膨脹之層並未如設計般膨脹，而無法充分確保氣密性。此外，在氧化膨脹處理時需要700℃以上之高溫製程也是問題。 However, according to the method described in Patent Document 1, when the oxidative expansion causes strong stress on the electrolyte membrane, the layer which is cracked or peeled off or oxidized and expanded does not expand as designed, and the airtightness cannot be sufficiently ensured. Sex. In addition, it is also a problem to require a high temperature process of 700 ° C or higher in the oxidative expansion treatment.
專利文獻1：日本特表2005-527370號公報 Patent Document 1: Japanese Patent Publication No. 2005-527370
本發明係為了解決固態氧化物燃料電池的電解質成膜之相關上述課題而創作者，其目的在於提供一種不必經高溫製程便可得到之氣密性優良的燃料電池用電解質、以及使用該種電解質之固態氧化物燃料電池、與其製造方法。 The present invention has been made in an effort to solve the above-described problems associated with electrolyte film formation of a solid oxide fuel cell, and an object of the present invention is to provide an electrolyte for a fuel cell which is excellent in airtightness which can be obtained without a high-temperature process, and the use of the electrolyte. Solid oxide fuel cell, and method of manufacturing the same.
本發明團隊為達成上述目的而反覆研究，結果發現以PLD法或濺鍍法等物理蒸鍍法所得到之發揮電解質功能之固體氧化物，藉由在其柱狀結晶間的間隙填充微粒子，便能達成上述目的，進而完成本發明。 In order to achieve the above object, the inventors of the present invention have found that the solid oxide functioning as an electrolyte obtained by a physical vapor deposition method such as a PLD method or a sputtering method is filled with fine particles by a gap between the columnar crystals. The above object can be achieved to complete the present invention.
本發明係基於上述知識，其特徵為：在具備 氧離子傳導性之固體氧化物的柱狀結晶間的間隙之厚度方向的一部分，填充有導電性材料、絕緣性材料、電解質材料中的至少一種類微粒子。此外，本發明之燃料電池用電解質，其特徵為：在具備氧離子傳導性之固體氧化物的柱狀結晶間的間隙之厚度方向的全域，填充有絕緣性材料、電解質材料中的至少一種類微粒子。 The present invention is based on the above knowledge and is characterized in that it is provided A part of the thickness direction of the gap between the columnar crystals of the oxygen-ion conductive solid oxide is filled with at least one type of fine particles of a conductive material, an insulating material, and an electrolyte material. Further, the electrolyte for a fuel cell of the present invention is characterized in that at least one of an insulating material and an electrolyte material is filled in the entire thickness direction of the gap between the columnar crystals of the solid oxide having oxygen ion conductivity. Microparticles.
此外，在上述固體氧化物的表面，更形成有上述微粒子所構成之層、或是形成至少一層具備柱狀結晶組織與氧離子傳導性之固體氧化物，也就是柱狀結晶組織的電解質層。 Further, on the surface of the solid oxide, a layer composed of the fine particles or at least one electrolyte layer having a columnar crystal structure and a solid oxide of oxygen ion conductivity, that is, a columnar crystal structure is formed.
又，本發明之固態氧化物燃料電池，係在多孔質燃料極與多孔質空氣極之間具備本發明之上述電解質。 Further, in the solid oxide fuel cell of the present invention, the electrolyte of the present invention is provided between the porous fuel electrode and the porous air electrode.
又，本發明之固態氧化物燃料電池之製造方法，其特徵為：包含：在多孔質電極上蒸鍍固體氧化物層之工程；及於上述固體氧化物層浸含散佈有微粒子之溶液並乾燥之工程；更可視需要，包含：在乾燥後的固體氧化物層的表面更塗布微粒子溶液並乾燥之工程；及在乾燥後的固體氧化物層之表面，更蒸鍍至少一層固體氧化物層之工程。 Further, a method for producing a solid oxide fuel cell of the present invention comprises: a step of depositing a solid oxide layer on a porous electrode; and impregnating the solid oxide layer with a solution in which fine particles are dispersed and drying Engineering; more as needed, including: coating the surface of the dried solid oxide layer with a fine particle solution and drying; and depositing at least one layer of solid oxide on the surface of the dried solid oxide layer engineering.
此外，本發明之燃料電池堆，其特徵為：將本發明之上述固態氧化物燃料電池層積複數個而成。 Further, a fuel cell stack according to the present invention is characterized in that the solid oxide fuel cell of the present invention is laminated in plural.
按照本發明，係針對具備氧離子傳導性的固體氧化物，做成在其柱狀結晶間的間隙的厚度方向一部分 或全域填充微粒子，故即使藉由PLD法或濺鍍法等物理蒸鍍法以較低溫度成膜的情形下，仍然能夠填埋柱狀結晶間的間隙，能夠確保作為電解質膜之氣密性。 According to the present invention, a solid oxide having oxygen ion conductivity is formed as a part of a thickness direction of a gap between column crystals thereof. In addition, even if the film is filled at a relatively low temperature by a physical vapor deposition method such as a PLD method or a sputtering method, the gap between the columnar crystals can be filled, and the gas tightness as the electrolyte membrane can be ensured. .
1‧‧‧燃料電池用電解質 1‧‧‧Electrolyte for fuel cells
C‧‧‧柱狀結晶(固體氧化物) C‧‧‧columnar crystals (solid oxides)
E‧‧‧多孔質電極 E‧‧‧Porous electrode
P‧‧‧微粒子 P‧‧‧Microparticles
S‧‧‧固體氧化物 S‧‧‧Solid oxides
Ld‧‧‧分散液 Ld‧‧‧Dispersion
Lp‧‧‧微粒子層 Lp‧‧‧microparticle layer
Ls‧‧‧固體氧化物層 Ls‧‧‧ solid oxide layer
[圖1](a)~(e)分別為本發明燃料電池用電解質之實施形態概念示意概略截面圖。 Fig. 1 (a) to (e) are schematic schematic cross-sectional views showing an embodiment of an electrolyte for a fuel cell of the present invention.
[圖2]圖1(a)及(b)所示之第1及第2實施形態燃料電池用電解質之製造步驟示意工程圖。 Fig. 2 is a schematic view showing a manufacturing procedure of the electrolyte for a fuel cell according to the first and second embodiments shown in Figs. 1(a) and 1(b).
[圖3]圖1(c)及(d)所示之第3及第4實施形態燃料電池用電解質之製造步驟示意工程圖。 Fig. 3 is a schematic view showing a manufacturing procedure of an electrolyte for a fuel cell according to third and fourth embodiments shown in Figs. 1 (c) and (d).
[圖4]圖1(e)所示之第5實施形態燃料電池用電解質之製造步驟示意工程圖。 Fig. 4 is a schematic view showing a manufacturing procedure of an electrolyte for a fuel cell according to a fifth embodiment shown in Fig. 1(e).
[圖5]藉由常溫下濺鍍法所形成之比較例1電解質(固體氧化物)的截面組織示意掃描型顯微鏡像。 [Fig. 5] A scanning microscope image of a cross-sectional structure of an electrolyte (solid oxide) of Comparative Example 1 formed by a sputtering method at normal temperature.
[圖6]將藉由常溫下濺鍍法所形成之固體氧化物施以YSZ微粒子填充處理之本發明實施例電解質之截面組織示意掃描型顯微鏡像。 Fig. 6 is a schematic scanning microscopic image of a cross-sectional structure of an electrolyte of an embodiment of the present invention in which a solid oxide formed by sputtering at a normal temperature is subjected to YSZ fine particle filling treatment.
[圖7]實施例中用於He洩漏強度測定之裝置構成示意概略圖。 Fig. 7 is a schematic view showing the configuration of an apparatus for measuring He leakage strength in the examples.
[圖8]將本發明實施例之燃料電池用電解質的氣體透過性，與未施以微粒子填充處理之比較例1與網版印刷法所得之比較例2加以比較之示意圖表。 Fig. 8 is a schematic view showing a gas permeability of an electrolyte for a fuel cell according to an embodiment of the present invention, a comparative example 1 which was not subjected to the fine particle filling treatment, and a comparative example 2 obtained by the screen printing method.
以下進一步詳細且具體說明本發明之燃料電池用電解質及其製造方法。另，本說明書中，「%」在未特別標註的情況下係指質量百分率。 Hereinafter, the electrolyte for a fuel cell of the present invention and a method for producing the same will be described in further detail. In addition, in the present specification, "%" means the mass percentage unless otherwise specified.
本發明之燃料電池用電解質，具有氧離子傳導性，發揮固體電解質功能之固體氧化物，在其柱狀結晶間的間隙的厚度方向一部分或厚度方向全域，填充有微粒子。 The electrolyte for a fuel cell of the present invention has a solid oxide function of oxygen ion conductivity and exhibits a solid electrolyte function, and is filled with fine particles in a part of the thickness direction of the gap between the columnar crystals or in the entire thickness direction.
也就是說，即使是以PLD法或濺鍍法等物理蒸鍍法以低溫度成膜之間隙多的柱狀結晶構造固體氧化物，藉由在該間隙填充微粒子，其氣密性會提升，而變成足以作為燃料電池用之電解質膜。是故，相較於以往能夠以更低溫度使電解質膜成膜，故能將金屬支撐型電池的金屬基板從耐熱合金換成廉價的金屬材料，且可使電解質膜及電極薄膜化，大幅削減材料成本。 In other words, even if the columnar crystal structure solid oxide having a large gap formed at a low temperature by a physical vapor deposition method such as a PLD method or a sputtering method is used, the airtightness is improved by filling the gap with the fine particles. It becomes an electrolyte membrane sufficient for use as a fuel cell. Therefore, the electrolyte membrane can be formed at a lower temperature than in the related art, so that the metal substrate of the metal-supported battery can be changed from a heat-resistant alloy to an inexpensive metal material, and the electrolyte membrane and the electrode can be thinned, and the membrane can be greatly reduced. Material costs.
圖1(a)~(e)分別為本發明燃料電池用電解質之實施形態模型示意概念概略截面圖，圖1(a)揭示其第1實施形態。 1(a) to 1(e) are schematic cross-sectional views showing a schematic diagram of an embodiment of an electrolyte for a fuel cell of the present invention, and Fig. 1(a) shows a first embodiment thereof.
第1實施形態之燃料電池用電解質1，如圖1(a)所示，主要是由固體氧化物所構成，該固體氧化物是在多孔質電極(燃料極或空氣極)E上藉由磁控濺鍍法(Magnetron Sputtering)等物理蒸鍍法而蒸鍍數μm厚度。 As shown in Fig. 1(a), the fuel cell electrolyte 1 of the first embodiment is mainly composed of a solid oxide which is magnetically supported on a porous electrode (fuel electrode or air electrode) E. A physical vapor deposition method such as a magnetron sputtering method is used to deposit a thickness of several μm.
該固體氧化物具備氧離子傳導性，發揮燃料電池用電 解質之功能，且具有柱狀結晶組織，在其柱狀結晶C間的間隙內，於其厚度方向一部分填充有微粒子P，藉此保持作為電解質層之氣密性。 The solid oxide has oxygen ion conductivity and functions as a fuel cell. The function of de-massing has a columnar crystal structure, and in the gap between the columnar crystals C, a part of the thickness P is filled with the fine particles P, thereby maintaining the airtightness as the electrolyte layer.
作為上述固體氧化物，可例舉具備氧離子傳導性，發揮固體電解質功能之氧化物，代表性之物如氧化釔安定氧化鋯(Yttria Stabilized Zirconia,YSZ：Zr1-xYxO2)。除了該YSZ以外，可以使用鈧安定氧化鋯(Scandium-Stabilized Zirconia,SSZ：Zr1-xScxO2)、氧化釤添加氧化鈰(Samarium-Doped Ceria,SDC：Ce1-xSmxO2)、氧化釓添加氧化鈰(Gadolinium-Doped Ceria,GDC：Ce1-xGdxO2)、鑭鍶鎵鎂(Lanthanum Strontium Gallate Magnesite,LSGM：La1-xSrxGa1-yMgyO3)等。 The solid oxide may, for example, be an oxide having oxygen ion conductivity and exhibiting a function of a solid electrolyte, and a typical material such as Yttria Stabilized Zirconia (YSZ: Zr 1-x Y x O 2 ). In addition to the YSZ, Scandium-Stabilized Zirconia (SSZ: Zr 1-x Sc x O 2 ), yttria-doped Ceria (SDC: Ce 1-x Sm x O 2 ) may be used. ), yttrium oxide added yttrium oxide (Gadolinium-Doped Ceria, GDC: Ce 1-x Gd x O 2 ), lanthanum gallium magnesium (Lanthanum Strontium Gallate Magnesite, LSGM: La 1-x Sr x Ga 1-y Mg y O 3 ) Wait.
另一方面，作為在上述固體氧化物的柱狀結晶C 間填充之微粒子P，可以使用絕緣性材料或電解質材料，但因其會曝露在燃料極及空氣極雙方的環境下，故需要對氧化/還原兩種環境有耐性。另，即使將絕緣性材料或電解質材料連結兩極間，也不會有短路之虞，故可填充至柱狀結晶C間的部分或全域。此外，本第1實施形態中，微粒子P會停留在固體氧化物的柱狀結晶間的間隙內一部分，而不會連結兩極間，故亦能運用在金屬等導電性材料。 On the other hand, as the columnar crystal C in the above solid oxide The intervening fine particles P may be made of an insulating material or an electrolyte material, but since they are exposed to the environment of both the fuel electrode and the air electrode, resistance to both the oxidation/reduction environment is required. Further, even if an insulating material or an electrolyte material is connected between the two electrodes, there is no short circuit, so that it can be filled in a portion or a whole region between the columnar crystals C. Further, in the first embodiment, the fine particles P remain in a part of the gap between the columnar crystals of the solid oxide, and do not connect between the two electrodes, so that they can be applied to a conductive material such as a metal.
絕緣性材料的具體例，例如有玻璃、雲母或高溫固力特(Thermiculite，註冊商標)等礦物、SiO2、Al2O3、MgO、Si3N4、Y2O3、ZrO2、AlN等陶瓷材料，但必需比 發揮電解質功能之固體氧化物還為高電阻體。 Specific examples of the insulating material include minerals such as glass, mica or high-temperature thermostat (registered trademark), SiO 2 , Al 2 O 3 , MgO, Si 3 N 4 , Y 2 O 3 , ZrO 2 , AlN. A ceramic material, but it must be a high-resistance body than a solid oxide that functions as an electrolyte.
作為電解質材料，可例舉YSZ、GDC、BiO2等螢石型化合物、LSGM等鈣鈦礦(Perovskite)化合物、磷灰石(Ln10(Si or Ge)6O27、Ln：La，Ce，Pr，Nd等鑭系元素)。此外，作為導電性材料，例如有Au(金)、Pt(白金)、Pd(鈀)、Rh(銠)等，但在運轉溫度或製造程序中，必須不會熔融、流動、氧化膨脹。 Examples of the electrolyte material include fluorite-type compounds such as YSZ, GDC, and BiO 2 , perovskite compounds such as LSGM, and apatite (Ln 10 (Si or Ge) 6 O 27 , Ln: La, Ce, and the like. Pr, Nd and other lanthanides). Further, examples of the conductive material include Au (gold), Pt (platinum), Pd (palladium), and Rh (yttrium). However, in the operating temperature or the manufacturing process, it is not necessary to melt, flow, or oxidize and swell.
另，上述各種材料中，作為微粒子P，理想是與作為電解質膜之固體氧化物為同種之電解質材料，或是熱膨脹率或熱傳導特性等特性近似之電解質材料。 Further, among the above various materials, the fine particles P are preferably electrolyte materials of the same kind as the solid oxide of the electrolyte membrane, or electrolyte materials similar in characteristics such as thermal expansion coefficient or heat conduction property.
圖1(b)揭示本發明燃料電池用電解質之第2實施形態，本形態之燃料電池用電解質1如圖所示，其具有之構造為，在多孔質電極E上以同樣方式形成之固體氧化物中，於其柱狀結晶C間的間隙內的厚度方向全域填充微粒子P。是故，相較於上述第1實施形態之電解質1，氣密性較優良。 Fig. 1(b) shows a second embodiment of the electrolyte for a fuel cell of the present invention. The fuel cell electrolyte 1 of the present embodiment has a structure in which solid oxidation is formed in the same manner on the porous electrode E. The fine particles P are filled in the entire thickness direction in the gap between the columnar crystals C. Therefore, compared with the electrolyte 1 of the above-described first embodiment, the airtightness is excellent.
本第2實施形態中，微粒子P係填充柱狀結晶C間的間隙全體，而將燃料極一空氣極間連結，故不可運用導電性材料來作為微粒子P之材料。除此之外，微粒子P所需之特性基本上如同上述。 In the second embodiment, the fine particles P are filled with the entire gap between the columnar crystals C, and the fuel electrode and the air electrode are connected to each other. Therefore, a conductive material cannot be used as the material of the fine particles P. In addition to this, the characteristics required for the fine particles P are substantially the same as described above.
上述第1及第2實施形態之電解質1，例如可藉由圖2所示之製程而製造。 The electrolyte 1 of the first and second embodiments described above can be produced, for example, by the process shown in Fig. 2 .
另，在此說明之例子，是在Ni-YSZ金屬瓷料(cermet)所構成之多孔質燃料極E上，蒸鍍YSZ以作為固體氧化 物，並在該固體氧化物的柱狀結晶間填充YSZ奈米粒子之情形。但，並非僅限定於該種組合，當然可運用上述各種材料。 Further, an example described here is to deposit YSZ as a solid oxide on a porous fuel electrode E composed of a Ni-YSZ cermet. And filling the YSZ nanoparticle between the columnar crystals of the solid oxide. However, it is not limited to this combination, and of course, the above various materials can be used.
首先，如圖2(a)所示，在Ni-YSZ所構成之多孔質燃料極E上，藉由物理蒸鍍法，例如DC磁控濺鍍法，使由YSZ所構成之發揮電解質功能之固體氧化物S成膜。 First, as shown in Fig. 2(a), on the porous fuel electrode E composed of Ni-YSZ, an electrolyte function is formed by YSZ by a physical vapor deposition method such as DC magnetron sputtering. The solid oxide S is formed into a film.
此時，例如採用常溫、Ar/O2氣體供應下60分鐘之成膜條件，藉此，能夠將固體氧化物S形成2μm厚度。 At this time, for example, film formation conditions under normal temperature and Ar/O 2 gas supply for 60 minutes are employed, whereby the solid oxide S can be formed to have a thickness of 2 μm.
接著如圖2(b)所示，將成膜有固體氧化物S之多孔質燃料極E載置於真空裝置上，於固體氧化物S的表面塗布分散液Ld以作為微粒子，該分散液Ld是將粒徑30~40nm的YSZ奈米粒子散佈於水中，再藉由真空泵浦抽吸，藉此使上述分散液浸含於固體氧化物S的柱狀結晶間。 Next, as shown in Fig. 2(b), the porous fuel electrode E on which the solid oxide S is formed is placed on a vacuum apparatus, and the dispersion liquid Ld is applied as a fine particle on the surface of the solid oxide S, and the dispersion liquid Ld The YSZ nanoparticle having a particle diameter of 30 to 40 nm is dispersed in water, and the liquid is pumped by vacuum pumping to thereby immerse the dispersion in the columnar crystal of the solid oxide S.
另，已確認使上述分散液Ld的固形物含量濃度在30%以上，例如50%左右，藉此會成為適合之浸含效率。此外，抽吸時之真空度，只要比大氣壓還低壓0.07MPa程度即可。 Further, it has been confirmed that the solid content concentration of the dispersion liquid Ld is 30% or more, for example, about 50%, whereby the impregnation efficiency is suitable. Further, the degree of vacuum at the time of suction may be as low as 0.07 MPa lower than atmospheric pressure.
此時，分散液Ld中的微粒子粒徑，從浸含效率的觀點看來，理想是比所成膜之固體氧化物S的柱狀結晶C間隔還小。 At this time, the particle diameter of the fine particles in the dispersion liquid Ld is preferably smaller than the columnar crystal C of the solid oxide S to be formed from the viewpoint of the impregnation efficiency.
此外，從抑制浸含後的體積變化，防止電解質剝離或裂開的觀點看來，上述微粒子理想是如上述YSZ般，以 最終成分之狀態散佈於液中。 Further, from the viewpoint of suppressing volume change after impregnation and preventing peeling or cracking of the electrolyte, the above fine particles are desirably as in the above-described YSZ, The state of the final component is dispersed in the liquid.
接著，以150℃使其乾燥20分鐘左右，藉此，所浸含之分散液水分會被除去，如圖2(c)所示，可得到本發明第1實施形態之燃料電池用電解質1，其作為微粒子P之YSZ奈米粒子部分填充於固體氧化物S的柱狀結晶C間而成。 Then, it is dried at 150 ° C for about 20 minutes, whereby the water of the dispersion liquid to be impregnated is removed, and as shown in Fig. 2 (c), the electrolyte 1 for a fuel cell according to the first embodiment of the present invention can be obtained. The YSZ nanoparticle as the fine particles P is partially filled between the columnar crystals C of the solid oxide S.
此外，在圖2(b)所示之分散液Ld塗布工程中，增加分散液Ld的塗布量，使YSZ奈米粒子所構成之微粒子P填充至固體氧化物S的柱狀結晶C間的間隙全域，藉此，如圖2(d)所示，可得到本發明第2實施形態(圖1(b))之燃料電池用電解質1。 Further, in the dispersion liquid Ld coating process shown in Fig. 2(b), the coating amount of the dispersion liquid Ld is increased, and the fine particles P composed of the YSZ nanoparticles are filled in the gap between the columnar crystals C of the solid oxide S. As a whole, as shown in Fig. 2(d), the fuel cell electrolyte 1 of the second embodiment (Fig. 1 (b)) of the present invention can be obtained.
上述揭示之例子，係使用Ni-YSZ金屬瓷料所構成之燃料極來作為多孔質電極E，但除此之外，作為燃料極亦可使用Ni(鎳)與YSZ或SDC、GDC之混合金屬瓷料、以及將Ni替換為Cu(銅)Pt之金屬瓷料、或使用含Ni、Cu、Pt的至少2種之混合物金屬瓷料。此外，作為空氣極，例如可使用LSM(La1-xSrxMnO3)、LSCF(La1-xSrxCo1-yFeyO3)、SSC(SmxSr1-xCoO3)、LSF(LaxSr1-xFeO3)、BSCF(BaxSr1-xCoyFe1-yO3)、LNF(LaNi1-xFexO3)、SSC(SmxSr1-xCoO3)等鈣鈦礦系化合物，或La2NiO4、(LaSr)2(COFe)O4等氧化物所構成之多孔質材料。 In the above-described example, the fuel electrode composed of Ni-YSZ metal ceramic is used as the porous electrode E. However, as the fuel electrode, a mixed metal of Ni (nickel) and YSZ or SDC or GDC may be used. An porcelain material, a metal ceramic material in which Ni is replaced with Cu (copper) Pt, or a metal ceramic material containing at least two kinds of Ni, Cu, and Pt. Further, as the air electrode, for example, LSM (La 1-x Sr x MnO 3 ), LSCF (La 1-x Sr x Co 1-y Fe y O 3 ), SSC (Sm x Sr 1-x CoO 3 ) can be used. , LSF (La x Sr 1-x FeO 3 ), BSCF (Ba x Sr 1-x Co y Fe 1-y O 3 ), LNF (LaNi 1-x Fe x O 3 ), SSC (Sm x Sr 1- a porous material such as a perovskite compound such as x CoO 3 ) or an oxide such as La 2 NiO 4 or (LaSr) 2 (COFe)O 4 .
另，作為構成電解質1之固體氧化物S，如果是選用YSZ時，為了防止與空氣極發生反應，必須在它們之間設置中間層。作為此類中間層，可使用SDC、 YDC(Yttria-Doped Ceria，氧化釔添加氧化鈰)、GDC等氧化鈰系材料。 Further, as the solid oxide S constituting the electrolyte 1, if YSZ is selected, an intermediate layer must be provided between them in order to prevent reaction with the air electrode. As such an intermediate layer, you can use SDC, YDC (Yttria-Doped Ceria, yttrium oxide added yttrium oxide), yttrium oxide materials such as GDC.
圖1(c)揭示本發明燃料電池用電解質之第3實施形態，本形態之燃料電池用電解質1如圖所示，其具有之構造為，在柱狀結晶C間的間隙內的厚度方向一部分填充有微粒子P狀態之固體氧化物的表面上，更具備微粒子所構成之層Lp。該實施形態之電解質1的氣密性，相較於上述第1實施形態之電解質1較優良。 Fig. 1 (c) shows a third embodiment of the electrolyte for a fuel cell of the present invention. The fuel cell electrolyte 1 of the present embodiment has a structure in which a part of the thickness direction in the gap between the columnar crystals C is formed. The surface of the solid oxide filled with the fine particles P state is further provided with a layer Lp composed of fine particles. The airtightness of the electrolyte 1 of this embodiment is superior to that of the electrolyte 1 of the above-described first embodiment.
燃料電池用電解質1需具氧離子傳導性，亦即從空氣極供給氧離子至燃料極。是故，至少構成上述層Lp之微粒子，必須使用不阻礙氧離子傳導性之材料，上述微粒子材料中，可使用除絕緣性材料或導電性材料以外之電解質材料。 The electrolyte 1 for a fuel cell needs to have oxygen ion conductivity, that is, supply oxygen ions from the air electrode to the fuel electrode. Therefore, at least the material constituting the layer Lp must be made of a material that does not inhibit oxygen ion conductivity, and an electrolyte material other than the insulating material or the conductive material can be used as the fine particle material.
但，構成層Lp之微粒子，與填充至柱狀結晶C間的間隙之微粒子P並不一定要相同，只要構成層Lp之微粒子具備氧離子傳導性，那麼填充至間隙的微粒子P亦可使用先前列舉之絕緣性材料或導電性材料。 However, the fine particles P constituting the layer Lp are not necessarily the same as the fine particles P filled in the gap between the columnar crystals C, and the fine particles P filled in the gap may be used as long as the fine particles constituting the layer Lp have oxygen ion conductivity. Listed as insulating materials or conductive materials.
圖1(d)揭示本發明燃料電池用電解質之第4實施形態，本形態之燃料電池用電解質1如圖所示，其具有之構造為，在柱狀結晶C間的間隙內的厚度方向全域填充有微粒子P狀態之固體氧化物的表面上，更具備微粒子所構成之層Lp。 Fig. 1 (d) shows a fourth embodiment of the electrolyte for a fuel cell of the present invention. The fuel cell electrolyte 1 of the present embodiment has a structure in which the thickness is in the gap between the columnar crystals C. The surface of the solid oxide filled with the fine particles P state is further provided with a layer Lp composed of fine particles.
也就是說，第4實施形態是在第2實施形態之固體氧化物的表面上更形成微粒子層Lp，該實施形態 之電解質1的氣密性，相較於上述第2及第3實施形態之電解質1較優良。 In other words, in the fourth embodiment, the fine particle layer Lp is further formed on the surface of the solid oxide of the second embodiment. The airtightness of the electrolyte 1 is superior to that of the electrolytes 1 of the second and third embodiments described above.
另，該實施形態中，如同第2實施形態般，微粒子P係填滿柱狀結晶C間的間隙全體，而將燃料極一空氣極間連結，故必須使用導電性材料以外之絕緣性材料或電解質材料來作為微粒子P的材料。此外，作為微粒子層Lp之材料，基本上可使用如同上述第3實施形態者。 Further, in this embodiment, as in the second embodiment, the fine particles P fill the entire gap between the columnar crystals C and connect the fuel electrode and the air electrode. Therefore, it is necessary to use an insulating material other than the conductive material or The electrolyte material serves as a material of the fine particles P. Further, as the material of the fine particle layer Lp, basically, the third embodiment as described above can be used.
上述第3及第4實施形態之電解質1，例如可藉由圖3所示之製程而製造。 The electrolyte 1 of the third and fourth embodiments described above can be produced, for example, by the process shown in FIG.
首先，如圖3(a)所示，如同第1及第2實施形態之情形，在多孔質燃料極E上使YSZ成膜，以作為發揮電解質功能之固體氧化物S。 First, as shown in Fig. 3 (a), as in the case of the first and second embodiments, YSZ is formed on the porous fuel electrode E as a solid oxide S which functions as an electrolyte.
接著如圖3(b)所示，塗布將YSZ奈米粒子散佈於水中而成之分散液Ld，藉由同樣的真空泵浦來抽吸，藉此使上述分散液浸含於固體氧化物S的柱狀結晶C間，同樣地以150℃使其乾燥20分鐘左右。 Next, as shown in FIG. 3(b), a dispersion Ld obtained by dispersing YSZ nanoparticles in water is applied, and suctioned by the same vacuum pump, whereby the dispersion is impregnated into the solid oxide S. The columnar crystals C were similarly dried at 150 ° C for about 20 minutes.
如此一來，如圖3(c)所示，YSZ奈米粒子P會部分填充於固體氧化物S的柱狀結晶C間，而得到如同第1實施形態之電解質1。 As a result, as shown in Fig. 3(c), the YSZ nanoparticle P is partially filled between the columnar crystals C of the solid oxide S to obtain the electrolyte 1 as in the first embodiment.
接著，在柱狀結晶C間部分填充有YSZ奈米粒子P之狀態的固體氧化物S的表面上，如圖3(d)所示，例如藉由旋轉塗布機再度塗布YSZ奈米粒子的分散液Ld，以150℃使其乾燥20分鐘左右，藉此，可得到如圖1(c)所示之第3實施形態之燃料電池用電解質1。 Next, on the surface of the solid oxide S in which the YSZ nanoparticle P is partially filled between the columnar crystals C, as shown in FIG. 3(d), the dispersion of the YSZ nanoparticle is recoated by, for example, a spin coater. The liquid Ld was dried at 150 ° C for about 20 minutes, whereby the fuel cell electrolyte 1 of the third embodiment shown in Fig. 1 (c) was obtained.
另，當然，在圖3(b)所示之分散液Ld塗布工程中，增加分散液Ld的塗布量，使YSZ微粒子P填充至固體氧化物S的柱狀結晶C間的間隙全域10，藉此，可得到如圖1(d)所示之第4實施形態之燃料電池用電解質1。 Further, of course, in the dispersion liquid Ld coating process shown in FIG. 3(b), the coating amount of the dispersion liquid Ld is increased, and the YSZ fine particles P are filled in the entire gap 10 between the columnar crystals C of the solid oxide S. Thus, the fuel cell electrolyte 1 of the fourth embodiment shown in Fig. 1(d) can be obtained.
圖1(e)揭示本發明燃料電池用電解質之第5 實施形態。 Figure 1 (e) shows the fifth of the electrolyte for a fuel cell of the present invention Implementation form.
本形態之燃料電池用電解質1，其具有之構造為，在柱狀結晶C間的間隙內的厚度方向一部分或全域(圖中揭示填充全域之情形)填充有微粒子P狀態下之固體氧化物的表面上，更具備發揮電解質功能之固體氧化物所構成之層Ls。 The fuel cell electrolyte 1 of the present aspect has a structure in which a part or a whole of the thickness direction in the gap between the columnar crystals C (in the case where the filling of the whole region is disclosed) is filled with the solid oxide in the state of the fine particles P. On the surface, a layer Ls composed of a solid oxide exhibiting an electrolyte function is further provided.
也就是說，本第5實施形態是在第1或第2實施形態之固體氧化物的表面上更形成固體氧化物所構成之電解質層Ls，該實施形態之電解質1的氣密性，至少相較於上述第1實施形態之電解質1較優良。此時，藉由使上述固體氧化物層Ls成膜多數次，亦可做成複層構造。 In other words, the fifth embodiment is an electrolyte layer Ls formed by forming a solid oxide on the surface of the solid oxide according to the first or second embodiment, and the electrolyte 1 of the embodiment has at least a gas-tightness. It is superior to the electrolyte 1 of the above-described first embodiment. At this time, by forming the solid oxide layer Ls a plurality of times, it is also possible to form a multi-layer structure.
是故，該第5實施形態之燃料電池用電解質1，其氣密性至少相較於上述第1實施形態較優良，且上述固體氧化物層Ls具有氧離子傳導性與絕緣性，故能夠擴大微粒子P的材料選擇性。 Therefore, the fuel cell electrolyte 1 of the fifth embodiment is excellent in airtightness at least as compared with the first embodiment, and the solid oxide layer Ls has oxygen ion conductivity and insulation properties, so that it can be expanded. Material selectivity of the microparticles P.
也就是說，在該電解質1上形成對極時，由於上述固體氧化物層LS的絕緣性，使得兩極間被電性絕緣，故也能夠使用導電性材料來作為微粒子P，可使用如 同第1實施形態情形般之絕緣性材料或電解質材料、導電性材料。 In other words, when the counter electrode is formed on the electrolyte 1, the insulating property of the solid oxide layer LS is electrically insulated between the electrodes. Therefore, a conductive material can be used as the fine particles P. An insulating material, an electrolyte material, or a conductive material as in the case of the first embodiment.
又，微粒子P會因固體氧化物層Ls而僅會曝露在燃料極及空氣極其中一方的環境下，故只要對氧化及還原環境其中一方具有耐性即足夠，故能夠運用燃料極材料或空氣極材料來作為微粒子P。亦即，當該電解質1形成於燃料極上時可使用燃料極材料、當形成於空氣極上時可使用空氣極材料來作為微粒子P之材料。 Further, since the fine particles P are exposed only to the environment of one of the fuel electrode and the air electrode due to the solid oxide layer Ls, it is sufficient to have resistance to one of the oxidation and reduction environments, so that the fuel electrode material or the air electrode can be used. The material comes as microparticles P. That is, the fuel electrode material may be used when the electrolyte 1 is formed on the fuel electrode, and the air electrode material may be used as the material of the fine particles P when formed on the air electrode.
該種第5實施形態之電解質1，例如可藉由圖4所示之製程而製造。 The electrolyte 1 of the fifth embodiment can be produced, for example, by the process shown in Fig. 4 .
也就是說，如圖4(a)~(c)所示，重複進行如同第1~第4實施形態情形之步驟，藉此，在多孔質燃料極E上形成YSZ微粒子P部分填充於柱狀結晶C間的間隙內之固體氧化物S。 In other words, as shown in Figs. 4(a) to 4(c), the steps of the first to fourth embodiments are repeated, whereby the YSZ fine particles P are partially formed on the porous fuel electrode E and filled in a columnar shape. The solid oxide S in the gap between the crystals C.
接著，在其表面上依據與圖4(a)工程相同之條件，使YSZ所構成之固體氧化物層Ls濺鍍成膜，藉此，可得到圖4(d)所示之第5實施形態之燃料電池用電解質1。此時，藉由使上述固體氧化物層Ls反覆成膜複數次，亦可將該固體氧化物層Ls做成複層構造。 Then, on the surface thereof, the solid oxide layer Ls composed of YSZ is sputter-deposited on the surface under the same conditions as those in Fig. 4(a), whereby the fifth embodiment shown in Fig. 4(d) can be obtained. Electrolyte 1 for fuel cell. At this time, the solid oxide layer Ls may be formed into a multi-layer structure by repeatedly forming the solid oxide layer Ls over the film.
我們知道，一般而言以濺鍍法所得之蒸鍍膜，依據欲成膜之基材面表面狀態不同，會大大地左右其形態、特性。此處所蒸鍍之固體氧化物層Ls，由於上述固體氧化物S表面的氣孔被微粒子P填充而變小，故氣密性會成為比最初形成之固體氧化物S還來得高。 As is known, in general, the vapor deposited film obtained by the sputtering method greatly differs in shape and characteristics depending on the surface state of the substrate on which the film is to be formed. In the solid oxide layer Ls deposited here, since the pores on the surface of the solid oxide S are filled with the fine particles P, the airtightness is higher than that of the solid oxide S formed first.
另，在圖4(b)所示之分散液Ld塗布工程中，如果增加分散液Ld的塗布量，使YSZ微粒子P填充至固體氧化物S的柱狀結晶C間的間隙全域，那麼可得到如圖1(e)所示之形態之燃料電池用電解質1。 Further, in the dispersion liquid Ld coating process shown in FIG. 4(b), if the coating amount of the dispersion liquid Ld is increased and the YSZ fine particles P are filled in the entire gap between the columnar crystals C of the solid oxide S, then An electrolyte 1 for a fuel cell in the form shown in Fig. 1(e).
以下根據實施例來具體說明本發明，但本發明當然不被該類實施例所限定。 The present invention will be specifically described below based on examples, but the present invention is of course not limited by such examples.
依照圖2所示之工程，在多孔質燃料電極上形成如圖1(a)所示之第1實施形態之燃料電池用電解質，以作為本發明之實施例。首先，使用DC磁控濺鍍法(常溫、Ar/O2氣體供應)，在Ni-YSZ所構成之多孔質燃料極E上使YSZ成膜60分鐘，藉此，在該燃料極E表面形成由YSZ所構成之厚度2μm的固體氧化物S(參照圖2(a))。 According to the process shown in Fig. 2, the electrolyte for a fuel cell according to the first embodiment shown in Fig. 1(a) is formed on the porous fuel electrode as an embodiment of the present invention. First, YSZ is formed on the porous fuel electrode E composed of Ni-YSZ by DC magnetron sputtering (normal temperature, Ar/O 2 gas supply) for 60 minutes, thereby forming a surface of the fuel electrode E. A solid oxide S having a thickness of 2 μm composed of YSZ (see Fig. 2(a)).
另，所得到的固體氧化物S的柱狀結晶C之結晶間隔，最大為1μm左右。 Further, the crystal separation interval of the columnar crystal C of the obtained solid oxide S is at most about 1 μm.
接著，將平均粒徑35nm的YSZ奈米粒子散佈於水中而使質量比成為50%之分散液Ld塗布於上述固體氧化物S表面，藉由真空泵浦抽吸，使該分散液Ld浸含於固體氧化物S的柱狀結晶C間(參照圖2(b))。接著，將其以150℃乾燥20分鐘。 Next, YSZ nanoparticles having an average particle diameter of 35 nm are dispersed in water, and a dispersion Ld having a mass ratio of 50% is applied onto the surface of the solid oxide S, and the dispersion Ld is impregnated by vacuum pumping. The columnar crystals C of the solid oxide S (see Fig. 2(b)). Next, it was dried at 150 ° C for 20 minutes.
如此一來，便得到本發明之燃料電池用電解質1，其 YSZ微粒子P部分填充於固體氧化物S的柱狀結晶C的間隙內而成(圖2(C)參照)。 In this way, the electrolyte 1 for a fuel cell of the present invention is obtained. The YSZ fine particles P are partially filled in the gap of the columnar crystal C of the solid oxide S (refer to FIG. 2(C)).
如圖2(a)所示，以相同的DC磁控濺鍍法，在Ni-YSZ所構成之多孔質燃料極E表面，同樣地形成由YSZ所構成之厚度2μm的固體氧化物S，不使其浸含於分散液Ld，而以原本形態作為比較例1之電解質。 As shown in Fig. 2(a), a solid oxide S having a thickness of 2 μm composed of YSZ is formed in the same manner on the surface of the porous fuel electrode E composed of Ni-YSZ by the same DC magnetron sputtering method. This was impregnated into the dispersion liquid Ld, and the original form was used as the electrolyte of Comparative Example 1.
在Ni-YSZ所構成之多孔質燃料極E表面，將YSZ85%、作為黏結劑之纖維素5%、以及作為分散劑之乙酸丁酯10%混合而成之電解質糊膏予以網版印刷，在大氣中乾燥。 On the surface of the porous fuel electrode E composed of Ni-YSZ, an electrolyte paste obtained by mixing YSZ 85%, 5% cellulose as a binder, and 10% butyl acetate as a dispersing agent is screen-printed. Dry in the atmosphere.
接著施以1350℃×5小時、及1100℃×2小時之燒成，藉此，在上述多孔質燃料極E上形成5μm厚度之由YSZ所構成之電解質，將其作為比較例2之電解質。 Subsequently, firing was performed at 1,350 ° C for 5 hours and at 1,100 ° C for 2 hours, whereby an electrolyte composed of YSZ having a thickness of 5 μm was formed on the porous fuel electrode E, and this was used as the electrolyte of Comparative Example 2.
圖5及圖6分別揭示依上述比較例1及實施例1所得之電解質截面的電子顯微鏡組織，在以常溫下DC磁控濺鍍法所得之YSZ所構成之固體氧化物(電解質層)中，如圖5中圈起處所示，可確認柱狀結晶間有間隙存在。 5 and FIG. 6 respectively disclose an electron microscope structure of the electrolyte cross section obtained in the above Comparative Example 1 and Example 1, in a solid oxide (electrolyte layer) composed of YSZ obtained by DC magnetron sputtering at normal temperature. As shown in the circle in Fig. 5, it was confirmed that a gap existed between the columnar crystals.
相對於此，藉由對上述固體氧化物施以含YSZ微粒子之分散液Ld浸含處理，如圖6中箭號所示，可看出柱狀結晶間的間隙已被YSZ微粒子填充。 On the other hand, by impregnating the solid oxide with the dispersion of the YSZ-containing fine particles Ld, as shown by the arrow in Fig. 6, it can be seen that the gap between the columnar crystals has been filled with the YSZ fine particles.
針對上述實施例1、比較例1及比較例2所得之電解質的氣密性，藉由測定其He洩漏強度來評估。 The airtightness of the electrolyte obtained in the above Example 1, Comparative Example 1, and Comparative Example 2 was evaluated by measuring the He leak strength.
氣密性評估是藉由圖7所示之裝置，以真空噴吹法，訂測試埠壓為6Pa、供應之He流量為100mI/min.，使用90°磁偏轉質譜儀作為檢測器。此外，洩漏強度係針對僅有多孔質燃料極之狀態(固體氧化物成膜前)、固體氧化物(電解質)成膜後之狀態、以及對固體氧化物填充微粒子後之狀態(實施例1)等各階段進行測定。其結果一併揭示於圖8。 The airtightness evaluation was carried out by a vacuum injection method using a device shown in Fig. 7, and the test pressure was 6 Pa, the supplied He flow was 100 mI/min., and a 90° magnetic deflection mass spectrometer was used as a detector. Further, the leak strength is a state in which only the porous fuel electrode is present (before the solid oxide film formation), a state in which the solid oxide (electrolyte) is formed, and a state in which the solid oxide is filled with the fine particles (Example 1). The measurement is performed at each stage. The results are also shown in Figure 8.
從圖8所示結果中可知，僅以常溫下DC磁控濺鍍法使YSZ成膜之比較例1電解質，其He洩漏強度高，結果氣密性差。相對於此，在以同樣方式成膜之固體氧化物S上塗布YSZ微粒子之分散液，而將YSZ微粒子填充於柱狀結晶間之實施例1電解質，相較於以網版印刷-高溫燒成而得之比較例2電解質，可發現縱使膜厚較薄，但卻幾乎具備同等的氣密性。 As is clear from the results shown in Fig. 8, the electrolyte of Comparative Example 1 in which YSZ was formed only by DC magnetron sputtering at normal temperature had high He leakage strength, and as a result, airtightness was poor. On the other hand, the dispersion of YSZ fine particles was coated on the solid oxide S formed in the same manner, and the electrolyte of Example 1 in which the YSZ fine particles were filled between the columnar crystals was compared with the screen printing-high temperature firing. In the electrolyte of Comparative Example 2, it was found that even though the film thickness was thin, it was almost equivalent in airtightness.
是故，按照本發明，可達成製造程序的低溫化與電解質的薄膜化，有望減低材料成本、減低製造成本、使燃料電池薄膜化及將其層積之燃料電池堆小型化。 Therefore, according to the present invention, it is possible to achieve a low temperature of the manufacturing process and a thin film of the electrolyte, and it is expected to reduce the material cost, reduce the manufacturing cost, thin the fuel cell, and miniaturize the fuel cell stack.
1‧‧‧燃料電池用電解質 1‧‧‧Electrolyte for fuel cells
C‧‧‧柱狀結晶(固體氧化物) C‧‧‧columnar crystals (solid oxides)
E‧‧‧多孔質電極 E‧‧‧Porous electrode
P‧‧‧微粒子 P‧‧‧Microparticles
S‧‧‧固體氧化物 S‧‧‧Solid oxides
Lp‧‧‧微粒子層 Lp‧‧‧microparticle layer
Ls‧‧‧固體氧化物層 Ls‧‧‧ solid oxide layer
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