TWI718548B - Electrolyte preparation method of solid oxide fuel cell - Google Patents
Electrolyte preparation method of solid oxide fuel cell Download PDFInfo
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Abstract
一種固態氧化物燃料電池之電解質製備方法，包含有以下步驟：(A)：將一陶瓷氧化物以水或醇類溶劑進行球磨，120-225rpm，2-10小時；(B)：將步驟(A)產物50-85℃烘乾；(C)：將步驟(B)產物煆燒800-1400℃，4-12小時；(D)：將步驟(C)產物添加1-10wt%之氧化鎳並均勻混合，即得到一電解質粉末；步驟(E)：將該電解質粉末與水或醇類溶劑及一黏結劑混合，再球磨150-250rpm，2-10小時，得到一電解質懸浮液；步驟(F)：將該電解質懸浮液滴於一旋轉塗佈機之旋轉盤，並於該旋轉盤形成至少二層之電解質薄膜，將該至少二層之電解質薄膜以600-1200℃烘乾後，再以1400-1700℃燒結，得到一電解質薄膜。 A solid oxide fuel cell electrolyte preparation method, including the following steps: (A): ball mill a ceramic oxide with water or alcohol solvent, 120-225rpm, 2-10 hours; (B): step ( A) The product is dried at 50-85°C; (C): the product of step (B) is sintered at 800-1400°C for 4-12 hours; (D): the product of step (C) is added with 1-10wt% nickel oxide And mix uniformly to obtain an electrolyte powder; step (E): mix the electrolyte powder with water or alcohol solvent and a binder, and then ball mill at 150-250 rpm for 2-10 hours to obtain an electrolyte suspension; step ( F): Drop the electrolyte suspension on the rotating disk of a spin coater, and form at least two layers of electrolyte film on the rotating disk, and then dry the at least two layers of electrolyte film at 600-1200°C. Sintering at 1400-1700°C to obtain an electrolyte membrane.
Description
本發明係與燃料電池之製備方法有關，特別是指一種固態氧化物燃料電池之電解質製備方法。 The present invention is related to the preparation method of the fuel cell, in particular to a preparation method of the electrolyte of a solid oxide fuel cell.
燃料電池有別於一般電池係將電能儲存後供電，燃料電池主要是在高溫工作環境下，以電極將反應氣體進行氧化還原反應，同時釋放電子、離子、熱能，只需持續供給燃料，氧化還原反應便能持續進行，電力將能不間斷地輸出。 The fuel cell is different from the general battery system that stores electric energy and supplies power. The fuel cell mainly uses electrodes to perform oxidation-reduction reactions in high-temperature working environment, and releases electrons, ions, and heat at the same time. It only needs to continue to supply fuel, oxidation-reduction The reaction will continue, and the power will be output uninterrupted.
燃料電池領域中的一種質子傳輸型固態氧化物燃料電池(Proton conducting solid oxide fuel cell,P-SOFC)，主要由陰極(Cathode)、陽極(Anode)與電解質(Electrolyte)所組成，一般來說，陰極材料係以鈣鈦礦為主，陽極材料以瓷金材料為主，電解質材料係以SrCeO3或BaCeO3為主，而因為BaCeO3為主材料的質子傳導性係優於以SrCeO3為主材料的質子傳導性，因此，多數會選擇以BaCeO3作為P-SOFC的電解質材料；其中，電解質的主要功能係連接陰陽兩極，並將陽極端所生成之質子傳輸至陰極端，因此，電解質需具備高質子傳導性與低電子傳導性，且於高溫操作溫度下必須有良好的化學穩定性與結構緻密性。 A proton conducting solid oxide fuel cell (P-SOFC) in the field of fuel cells is mainly composed of a cathode (Cathode), an anode (Anode) and an electrolyte (Electrolyte). Generally speaking, The cathode material is mainly perovskite, the anode material is mainly porcelain gold, and the electrolyte material is mainly SrCeO 3 or BaCeO 3 , and the proton conductivity of BaCeO 3 is better than that of SrCeO 3 The proton conductivity of the material, therefore, most will choose BaCeO 3 as the electrolyte material of P-SOFC; among them, the main function of the electrolyte is to connect the cathode and anode, and transmit the protons generated at the anode end to the cathode end. Therefore, the electrolyte needs It has high proton conductivity and low electronic conductivity, and must have good chemical stability and structural compactness at high operating temperatures.
其中主要影響結構緻密性的重要因素，乃在於電解質製備過程中，電解質粉末顆粒堆疊的均勻程度，若電解質粉末顆粒堆疊不均勻，容易在 燒結後留下孔洞與隙縫，這樣會造成質子傳輸的阻礙，會使電解質的質子傳導效率下滑。 Among them, the main factor that affects the compactness of the structure is the uniformity of the electrolyte powder particles stacking during the electrolyte preparation process. If the electrolyte powder particles are not uniformly stacked, it is easy to After sintering, pores and gaps are left, which will hinder the transport of protons and decrease the proton conduction efficiency of the electrolyte.
本發明之主要目的乃在於提供一種固態氧化物燃料電池之電解質製備方法，其可減少電解質出現孔洞與縫隙，藉此提升質子傳導效率。 The main purpose of the present invention is to provide a solid oxide fuel cell electrolyte preparation method, which can reduce pores and gaps in the electrolyte, thereby improving the proton conduction efficiency.
為了達成上述之目的，本發明提供之一種固態氧化物燃料電池之電解質製備方法，包含有以下步驟：(A)：將一陶瓷氧化物(ABO3)以水或醇類溶劑進行球磨，120-225rpm，2-10小時；(B)：將步驟(A)產物50-85℃烘乾；(C)：將步驟(B)產物煆燒800-1400℃，4-12小時；(D)：將步驟(C)產物添加1-10wt%之氧化鎳並均勻混合，即得到一電解質粉末；步驟(E)：將該電解質粉末與水或醇類溶劑及一黏結劑混合，再球磨150-250rpm，2-10小時，得到一電解質懸浮液；步驟(F)：將該電解質懸浮液滴於一旋轉塗佈機之旋轉盤，並於該旋轉盤形成至少二層之電解質薄膜，將該至少二層之電解質薄膜以600-1200℃烘乾後，再以1400-1700℃燒結，得到一電解質薄膜。 In order to achieve the above objective, the present invention provides a solid oxide fuel cell electrolyte preparation method, including the following steps: (A): ball mill a ceramic oxide (ABO 3 ) with water or alcohol solvent, 120- 225rpm, 2-10 hours; (B): dry the product of step (A) at 50-85°C; (C): burn the product of step (B) at 800-1400°C for 4-12 hours; (D): Add 1-10wt% nickel oxide to the product of step (C) and mix uniformly to obtain an electrolyte powder; step (E): mix the electrolyte powder with water or alcohol solvent and a binder, and then ball mill 150-250rpm , 2-10 hours to obtain an electrolyte suspension; step (F): drop the electrolyte suspension on the rotating disk of a spin coater, and form at least two layers of electrolyte film on the rotating disk, and the at least two The electrolyte film of the layer is dried at 600-1200°C and then sintered at 1400-1700°C to obtain an electrolyte film.
藉此，本發明所提供之一種固態氧化物燃料電池之電解質製備方法，可減少電解質出現孔洞與縫隙，藉此提升質子傳導效率。 Thereby, the electrolyte preparation method of the solid oxide fuel cell provided by the present invention can reduce the holes and gaps in the electrolyte, thereby improving the proton conduction efficiency.
10:固態氧化物燃料電池之電解質製備方法 10: Preparation method of electrolyte for solid oxide fuel cell
20:旋轉盤 20: Rotating disc
30:電解質薄膜 30: Electrolyte film
圖1係本發明較佳實施例之流程圖。 Figure 1 is a flowchart of a preferred embodiment of the present invention.
圖2係本發明較佳實施例之操作示意圖，顯示旋轉塗佈形成電解質薄膜的狀態。 Figure 2 is a schematic diagram of the operation of a preferred embodiment of the present invention, showing the state of spin coating to form an electrolyte thin film.
圖3係本發明一較佳實施例之XRD圖，分析步驟(C)產物之晶面。 Figure 3 is an XRD pattern of a preferred embodiment of the present invention, analyzing the crystal plane of the product of step (C).
圖4係本發明一較佳實施例之SEM圖，顯示步驟(C)產物之影像。 Figure 4 is an SEM image of a preferred embodiment of the present invention, showing the image of the product of step (C).
圖5係本發明一較佳實施例之統計圖，顯示粉末之粒徑分佈。 Figure 5 is a statistical diagram of a preferred embodiment of the present invention, showing the particle size distribution of the powder.
圖6係本發明一較佳實施例之SEM圖，顯示加入不同濃度的黏結劑之影像。 FIG. 6 is an SEM image of a preferred embodiment of the present invention, showing images of adding different concentrations of adhesive.
圖7係本發明一較佳實施例之SEM圖，顯示加入不同含量之電解質粉末的影像。 FIG. 7 is an SEM image of a preferred embodiment of the present invention, showing images of adding different amounts of electrolyte powder.
圖8係本發明一較佳實施例之SEM之剖面圖，顯示加入不同含量之電解質粉末的影像。 FIG. 8 is a cross-sectional view of an SEM of a preferred embodiment of the present invention, showing images of adding different amounts of electrolyte powder.
圖9係本發明一較佳實施例之統計圖，比較加入不同含量之電解質粉末的厚度。 Fig. 9 is a statistical chart of a preferred embodiment of the present invention, comparing the thickness of electrolyte powder with different contents.
圖10係本發明一較佳實施例之SEM之剖面圖，顯示不同層數之電解質薄膜。 FIG. 10 is a cross-sectional view of an SEM of a preferred embodiment of the present invention, showing electrolyte films of different layers.
圖11係本發明一較佳實施例之SEM頂側視角的二次電子影像圖，顯示添加不同含量之氧化鎳的影像。 FIG. 11 is a secondary electron image diagram of a top view angle of SEM of a preferred embodiment of the present invention, showing the image of adding different contents of nickel oxide.
圖12係本發明一較佳實施例之SEM頂側視角的背向散射電子影像圖，顯示添加不同含量之氧化鎳的影像。 FIG. 12 is a top-side SEM backscattered electron image diagram of a preferred embodiment of the present invention, showing the image of adding different contents of nickel oxide.
圖13係本發明一較佳實施例之統計圖，顯示單電池I-V性能曲線測量與分析。 FIG. 13 is a statistical diagram of a preferred embodiment of the present invention, showing the measurement and analysis of the I-V performance curve of a single cell.
圖14係本發明一較佳實施例之統計圖，顯示單電池之EIS測量與分析。 Figure 14 is a statistical diagram of a preferred embodiment of the present invention, showing the EIS measurement and analysis of a single cell.
為了詳細說明本發明之技術特點所在，茲舉以下一較佳實施例並配合圖式1-14說明如後，其中：如圖1所示，本發明一實施例提供之一種固態氧化物燃料電池之電解質製備方法10，包含有步驟(A)-(F)：步驟(A)：將一陶瓷氧化物以一醇類溶劑進行濕式球磨，170rpm，6小時；在本實施例中，該陶瓷氧化物為BaCe0.6Zr0.2Y0.2O3-δ(BCZY)。
In order to explain the technical features of the present invention in detail, the following is a preferred embodiment and is illustrated in conjunction with Figures 1-14. Among them: As shown in Figure 1, a solid oxide fuel cell provided by an embodiment of the present invention The
在其他實施例中，該陶瓷氧化物亦可為其他可組成鈣鈦礦結構(BCZY)之元素來作為實施，例如：鉀(K)、鈣(Ca)、鍶(Sr)、鋇(Ba)、鑭(La)，或上述元素之混合物：鋇鍶(BaxSry)、鋇鉀(BaxKy)、鑭鍶(LaxSry)等多元混合物，或例如：過度元素與鑭系元素，如：鋯(Zr)、釔(Y)、鐵(Fe)、錳(Mn)、鈷(Co)、銅(Cu)、(Cu)、錫(Zn)、銦(In)、鈰(Ce)、鐠(Pr)、釹(Nd)、鉺(Er)等，或者過度元素與鑭系元素之混合物，如：鈰鋯釔銦鉺錳(CesZrrYtInuErvMnw)等多元混合物，故該陶瓷氧化物之選擇，並不僅以本實施例為限。而球磨轉速可為120、130、140、150、160、180、190、200、210、220、225rpm，或於120-225rpm之間任一轉速來實施，球磨時間則為2、3、4、5、7、8、9、10小時，或於2-10小時內任一時間來實施，該醇類溶劑亦能以乙醇或水作為實施，故該醇類溶劑以及球磨條件，並不僅以本實施例為限。 In other embodiments, the ceramic oxide can also be other elements that can form a perovskite structure (BCZY) for implementation, such as potassium (K), calcium (Ca), strontium (Sr), barium (Ba) , Lanthanum (La), or mixtures of the above elements: barium strontium (BaxSry), barium potassium (BaxKy), lanthanum strontium (LaxSry), etc., or for example: transition elements and lanthanides, such as: zirconium (Zr), Yttrium (Y), iron (Fe), manganese (Mn), cobalt (Co), copper (Cu), (Cu), tin (Zn), indium (In), cerium (Ce), 鐠 (Pr), neodymium (Nd), erbium (Er), etc., or a mixture of transition elements and lanthanide elements, such as: cerium zirconium yttrium indium erbium manganese (CesZrrYtInuErvMnw) and other multi-component mixtures, so the choice of ceramic oxide is not only in this embodiment limit. The ball milling speed can be 120, 130, 140, 150, 160, 180, 190, 200, 210, 220, 225rpm, or any speed between 120-225rpm. The ball milling time is 2, 3, 4, 5, 7, 8, 9, 10 hours, or any time within 2-10 hours, the alcohol solvent can also be implemented with ethanol or water, so the alcohol solvent and ball milling conditions are not only based on the original The embodiment is limited.
步驟(B)將步驟(A)產物於65℃烘乾，在其他較佳實施例中，亦可於50、55、60、70、75、80、85℃，或於50-85℃之間任一溫度烘乾，故烘乾溫度不僅以本較佳實施例為限。 Step (B) Dry the product of step (A) at 65°C. In other preferred embodiments, it can also be at 50, 55, 60, 70, 75, 80, 85°C, or between 50-85°C It can be dried at any temperature, so the drying temperature is not limited to this preferred embodiment.
步驟(C)將步驟(B)產物煆燒1250℃，8小時。在其他實施例中，該煆燒溫度可選擇以800、900、1000、1100、1300、1400℃或800-1600℃區間任 一溫度來實施，而時間亦可於4、5、6、7、9、10、11、12小時，或4-12小時之間任一時間來實施，故步驟(C)中烘乾後產物煆燒的溫度及時間，並不以本實施例為限。 Step (C) The product of step (B) is sintered at 1250°C for 8 hours. In other embodiments, the sintering temperature can be selected to be in the range of 800, 900, 1000, 1100, 1300, 1400°C or 800-1600°C. It can be implemented at a temperature, and the time can also be implemented at any time between 4, 5, 6, 7, 9, 10, 11, 12 hours, or 4-12 hours, so the product after drying in step (C) The simmering temperature and time are not limited to this embodiment.
步驟(D)步驟(C)產物添加3%之氧化鎳(NiO)並均勻混合，即得到一電解質粉末。在其他實施例中，氧化鎳含量可為1、5、7、9、10wt%，或1-10wt%之區間任一含量，故氧化鎳之添加量並不僅以本實施例為限。 Step (D) Add 3% nickel oxide (NiO) to the product of step (C) and mix uniformly to obtain an electrolyte powder. In other embodiments, the content of nickel oxide can be 1, 5, 7, 9, 10 wt%, or any content in the range of 1-10 wt%, so the addition amount of nickel oxide is not limited to this embodiment.
步驟(E)將該電解質粉末與醇類溶劑及一黏結劑混合，以濕式球磨170rpm，6小時，得到一電解質懸浮液；在本實施例中，該電解質粉末、醇類溶劑及該黏結劑混合百分比為26：68：6，且該電解質懸浮液會再進行超音波震盪，以令該電解質懸浮液中團聚之顆粒分散，並減少其粒徑分布；另外，該醇類溶劑為乙醇，該黏結劑為聚乙烯吡咯烷酮(Polyvinylpyrrolidone,PVP)。在其他實施例中，該電解質粉末及該黏結劑混合百分比可為13：3，同樣能減少電解質出現孔洞與縫隙的情況，故該電解質粉末該黏結劑之配方比例，不僅以本實施例為限；另外，若該電解質懸浮液中沒有團聚之顆粒分散，或團聚之情況於可接受範圍內，超音波震盪即可省略，故將該電解質溶液進行超音波震盪，並非本發明之必要條件，而該醇類溶劑能以水或異丙醇為實施，該黏結劑則能以聚乙烯醇(Polyvinyl alcohol,PVA)作為實施，故該醇類溶劑及該黏結劑，也不以本較佳實施例為限；而球磨轉速可為150、160、180、190、200、210、220、230、240、250rpm，或於150-250rpm之間任一轉速來實施，球磨時間則為2、3、4、5、7、8、9、10小時，或於2-10小時內任一時間來實施，故球磨條件亦不僅以本實施例為限。 Step (E) Mix the electrolyte powder, alcohol solvent and a binder, and wet ball mill at 170 rpm for 6 hours to obtain an electrolyte suspension; in this embodiment, the electrolyte powder, alcohol solvent and the binder The mixing percentage is 26:68:6, and the electrolyte suspension will be subjected to ultrasonic vibration to disperse the agglomerated particles in the electrolyte suspension and reduce the particle size distribution; in addition, the alcohol solvent is ethanol, the The binding agent is Polyvinylpyrrolidone (PVP). In other embodiments, the mixing percentage of the electrolyte powder and the binder can be 13:3, which can also reduce the presence of holes and gaps in the electrolyte. Therefore, the formula ratio of the electrolyte powder and the binder is not limited to this embodiment. In addition, if there are no agglomerated particles dispersed in the electrolyte suspension, or the agglomeration is within an acceptable range, the ultrasonic vibration can be omitted, so ultrasonic vibration of the electrolyte solution is not a necessary condition of the present invention, and The alcohol solvent can be implemented with water or isopropanol, and the adhesive can be implemented with polyvinyl alcohol (PVA). Therefore, the alcohol solvent and the adhesive are not based on the preferred embodiment. The ball milling speed can be 150, 160, 180, 190, 200, 210, 220, 230, 240, 250rpm, or any speed between 150-250rpm. The ball milling time is 2, 3, 4 , 5, 7, 8, 9, 10 hours, or any time within 2-10 hours, so the ball milling conditions are not limited to this embodiment.
如圖2所示，步驟(F)將該電解質懸浮液滴於一電解質介面30，該電解質介面30係設於一旋轉塗佈機之旋轉盤20，該電解質介面30隨該旋轉盤20旋轉，，令該電解質旋浮液於該電解質介面30形成至少二層之電解質薄膜30，將該至少二層之電解質薄膜30以1000℃烘乾，藉以去除該黏結劑，再以1500℃燒結，即完成本發明；在其他實施例中，該至少二層之電解質薄膜30烘乾溫度能以600、700、800、900、1100、1200℃，或600-1200℃區間任一溫度作為實施，而燒結溫度能以1400、1600、1700℃，或1400-1700℃區間任一溫度作為實施，故烘乾及燒結溫度，並不僅以本實施例為限。在本實施例中，該電解質介面30係指陽極基板，但不限於此。
As shown in FIG. 2, step (F) drops the electrolyte suspension on an
以上係說明步驟方法與流程，以下說明依上述步驟方法得到之產物進行分析：煆燒粉末形貌分析：將步驟(C)所得之產物以XRD相鑑定分析，如圖3所示，確認形成BCZY鈣鈦礦立方晶體結構，主要出現6個明顯的主峰訊號，分別為(110)、(200)、(211)、(220)、(310)和(222)晶面；請再參閱如圖4所示，是將步驟(C)所得之產物以掃描式電子顯微鏡(Scanning Electron Microscope,SEM)影像分析，由SEM影像可觀察到粉末大小介於微米至次微米之間，其形狀為不規則狀；配置該電解質懸浮液之粉末若粒徑過大易造成粉末堆疊鬆散，粒徑過小則容易形成團聚使得漿料品質不佳，而經由雷射粒徑分析儀之分析，結果如圖5所示，粉末粒徑分佈均勻且大小約為100-600nm。 The above is the description of the steps and the process, the following descriptions are based on the analysis of the products obtained by the above steps: Analysis of the sintered powder morphology: The product obtained in step (C) is identified and analyzed by XRD, as shown in Figure 3, confirming the formation of BCZY Perovskite cubic crystal structure, there are mainly 6 obvious main peak signals, respectively (110), (200), (211), (220), (310) and (222) crystal planes; please refer to Figure 4 again As shown, the product obtained in step (C) is analyzed by scanning electron microscope (Scanning Electron Microscope, SEM). From the SEM image, it can be observed that the size of the powder is between micrometers and sub-micrometers, and its shape is irregular. ; If the particle size of the powder of the electrolyte suspension is too large, it will easily cause loose powder stacking, and if the particle size is too small, it will easily form agglomerations and make the slurry quality poor. Through the analysis of the laser particle size analyzer, the results are shown in Figure 5. The particle size distribution of the powder is uniform and the size is about 100-600nm.
微結構分析：以旋轉塗佈技術製備該電解質薄膜，其該電解質懸浮液之電解質粉末、該黏結劑與醇類溶劑之配比將影響薄膜品質，此外，進行旋轉塗佈時需注意噴塗距離、噴塗次數，噴塗距離將影響懸浮液附著於該旋轉 盤之均勻性。在沒有該黏結劑得該電解質懸浮液中，該電解質粉末受靜電作用影響，可能會產生團聚之現象，因此可添加該黏結劑，使其包覆粉末顆粒之表面並形成一能障，減少顆粒間之吸引力，避免粉末團聚，粉末顆粒間將以穩定的分散存在。 Microstructure analysis: The electrolyte film is prepared by spin coating technology. The ratio of the electrolyte powder of the electrolyte suspension, the binder and the alcohol solvent will affect the quality of the film. In addition, pay attention to the spraying distance, The number of spraying times and spraying distance will affect the uniformity of the suspension adhered to the rotating disk. In the electrolyte suspension without the binder, the electrolyte powder may be agglomerated under the influence of static electricity. Therefore, the binder can be added to cover the surface of the powder particles and form an energy barrier to reduce the particles. The attractive force between them prevents the powder from agglomerating, and the powder particles will exist in a stable dispersion.
於步驟(F)的該電解質薄膜，如圖6所示，配置不同該黏結劑濃度之該電解質懸浮液所塗佈之該電解質薄膜，並經過1500℃燒結；當該黏結劑濃度過低，粉末顆粒表面所覆蓋之黏結劑較少，有機會使得高分子鏈從一顆粒上延伸至另一顆粒上，因此粉末於懸浮液易形成鬆散之團聚體，且分散不均沉澱較快，此一不穩定之該電解質懸浮液所塗佈之該電解質薄膜品質不佳，當該電解質懸浮液塗佈至該旋轉盤時，如圖7(a)、(b)所示，粉末顆粒堆疊不均降低其堆積密度，使得燒結後易留下孔洞。然而如圖6(c)所示，適當該黏結劑之添加可避免該電解質粉末分佈不均，並維持高堆積密度，與其他濃度相比，燒結後之更為平整緻密。如圖6(d)所示，而當該黏結劑濃度過高時，粉末顆粒表面所覆蓋之該黏結劑較多，粉末顆粒之表面所包覆之阻擋層過厚，使得顆粒間距離變大，進而造成該電解質懸浮液塗佈至該旋轉盤時，粉末堆積不易形成最密堆積，使得燒結後該電解質薄膜易留下孔洞與細縫。 The electrolyte film in step (F), as shown in FIG. 6, is configured with the electrolyte film coated by the electrolyte suspension with different binder concentrations, and sintered at 1500°C; when the binder concentration is too low, the powder There is less binder covered on the particle surface, which has the opportunity to extend the polymer chain from one particle to another. Therefore, the powder is easy to form loose agglomerates in the suspension, and the uneven dispersion and precipitation are faster. The quality of the electrolyte film coated by the stable electrolyte suspension is not good. When the electrolyte suspension is applied to the rotating disk, as shown in Figure 7 (a) and (b), the uneven stacking of powder particles reduces it The bulk density makes it easy to leave holes after sintering. However, as shown in Figure 6(c), the proper addition of the binder can avoid uneven distribution of the electrolyte powder and maintain a high bulk density. Compared with other concentrations, the sintered product is smoother and denser. As shown in Figure 6(d), when the concentration of the binder is too high, the surface of the powder particles will cover more of the binder, and the barrier layer coated on the surface of the powder particles is too thick, making the distance between the particles larger Therefore, when the electrolyte suspension is applied to the rotating disk, the powder accumulation is not easy to form the densest accumulation, so that the electrolyte film is easy to leave holes and crevices after sintering.
由於該黏結劑濃度為6wt%之電解質懸浮液所塗佈仍有穿孔之存在，因此藉由固定該電解質粉末與該黏結劑比例為13：3，並調整該電解質懸浮液之粉末固含量來提升該電解質薄膜厚度，由圖7所示，可觀察到當粉末固含量過多或過少時，電解質表面仍有孔洞存在，因此該電解質懸浮液之固含量最佳參數介於26wt%至28.5wt%，並如圖8、9所示，隨著固含量增加該電解質薄膜層厚度將有所提升，21wt%、26wt%、28.5wt%、31wt%之該電解質懸浮液所 塗佈之厚度分別約為3.1μm、3.6μm、3.9μm、4.2μm。因而在相同緻密情況下，本發明以26wt%此組參數作為該電解質懸浮液配置。然而，如圖10所示，於SEM剖面圖可觀察到該電解質薄膜仍有孔洞存在，這些孔洞會成為使質子傳輸之阻礙，使其無法順利以最短距離傳遞到達陰極，此外，若電解質薄膜太薄又有孔洞時，網印陰極將有機會從電解質滲透至陽極，此狀況可能會導致陰陽極導通，產生短路現象。因此本發明藉由塗佈多層電解質增加厚度，由圖10所示，可觀察到其厚度與塗佈次數為正比關係，一層該電解質薄膜厚度約為3.6μm；二層為7.5μm；三層則約為10μm，當電解質薄膜厚度增加即可減少孔洞連通，避免陽極導通產生短路現象，同時避免發生穿氣問題。 Since the electrolyte suspension with a binder concentration of 6wt% still has perforations, it is improved by fixing the electrolyte powder to the binder ratio at 13:3 and adjusting the powder solid content of the electrolyte suspension The thickness of the electrolyte film, as shown in Figure 7, can be observed that when the powder solid content is too much or too little, there are still holes on the electrolyte surface. Therefore, the best parameter of the solid content of the electrolyte suspension is between 26wt% and 28.5wt%. And as shown in Figures 8 and 9, as the solid content increases, the thickness of the electrolyte membrane layer will increase. The electrolyte suspension of 21wt%, 26wt%, 28.5wt%, and 31wt% is The thickness of the coating is about 3.1μm, 3.6μm, 3.9μm, 4.2μm, respectively. Therefore, under the same dense condition, the present invention uses 26wt% as the electrolyte suspension configuration. However, as shown in Figure 10, it can be observed that the electrolyte membrane still has holes in the SEM cross-sectional view. These holes will become an obstacle to the transport of protons, making it impossible to smoothly transfer to the cathode in the shortest distance. In addition, if the electrolyte membrane is too large When it is thin and has holes, the screen-printed cathode will have a chance to penetrate from the electrolyte to the anode. This condition may cause the cathode and anode to conduct and cause a short circuit. Therefore, the present invention increases the thickness by coating multiple layers of electrolyte. As shown in Figure 10, it can be observed that the thickness is proportional to the number of coatings. The thickness of the electrolyte film for one layer is about 3.6μm; the thickness of the second layer is 7.5μm; It is about 10μm. When the thickness of the electrolyte film increases, it can reduce the connection of holes, avoid the short-circuit phenomenon caused by the anode conduction, and avoid the problem of gas penetration.
接著，將探討氧化鎳含量對該電解質薄膜之影響，由圖11、12所示，隨著氧化鎳添加量增加時，晶界之孔洞逐漸減少，且晶粒逐漸開始成長，當添加至3wt%時，晶粒成長趨勢較為顯著，而添加至10wt%時，晶粒成長趨勢逐漸趨於平緩，意味著氧化鎳之劑量將受到限制，並且當氧化鎳含量添加至5wt%以上時，如圖11(h)、(j)及圖12(h)、(j)所示晶粒中開始有孔洞生成，其主要原因為晶界之移動速度過快時，會造成晶界與孔洞分離之現象，此時晶界會自由移動，而孔洞將會被包覆於晶粒之中。此現象所生成之孔洞將無法於燒結過程中被消除，並且由於孔洞之生成，可能提高穿孔生成機率，且質子傳輸將受阻礙，進而導致性能衰退。因此氧化鎳較佳添加量為3wt%，其緻密性有明顯改善且晶粒有所成長，並且於晶粒中無孔洞生成。 Next, the influence of nickel oxide content on the electrolyte film will be discussed. As shown in Figures 11 and 12, as the amount of nickel oxide added increases, the pores in the grain boundary gradually decrease and the crystal grains gradually begin to grow. When added to 3wt% When adding 10wt%, the grain growth trend is more obvious, and when the content of nickel oxide is added to 10wt%, the grain growth trend gradually tends to be flat, which means that the dosage of nickel oxide will be limited, and when the content of nickel oxide is added to more than 5wt%, as shown in Figure 11 (h), (j) and Figure 12(h), (j) show that there are holes in the crystal grains. The main reason is that when the speed of the grain boundary is too fast, it will cause the separation of the grain boundary and the hole. At this time, the grain boundaries will move freely, and the holes will be covered in the grains. The pores generated by this phenomenon cannot be eliminated during the sintering process, and due to the generation of pores, the probability of perforation generation may be increased, and proton transmission will be hindered, resulting in performance degradation. Therefore, the preferable addition amount of nickel oxide is 3wt%, its compactness is obviously improved and the crystal grains are grown, and no holes are formed in the crystal grains.
單電池I-V性能曲線測量與分析：以旋轉塗佈法製備之單電池封裝於測台，陽極端以20cc/min通入氫氣，並將陽極之氧化鎳還原成金屬Ni後，於陽極端以200cc/min通入氫氣與陰極端以600cc/min通入空氣(21% N2+79% O2)，並於800℃、700℃、600℃、550℃量測電池性能。如圖13(a)所示，為雙層該電解質薄膜之單電池且使用La0.6Sr0.4Co0.8Fe0.2O3(LSCF)作為陰極，於800℃測得之開路電壓(OCV)為0.35V，其電壓值與理論值相差甚遠，代表電解質結構不夠緻密，仍有孔隙存在，導致反應氣體從電解質產生穿氣問題，並且於800℃下最高功率密度為5.93mW/cm2，此能量密度偏低，若將電解質改善將有效提升電池性能。為了避免電解質連通孔洞導致漏氣狀況發生，故將塗佈該電解質薄膜之次數提升至三層，圖13(b)為三層該電解質薄膜之單電池且使用LSCF作為陰極，於800℃測得之開路電壓(OCV)為0.99V，與理論值~1.0V相近，表示電解質足夠緻密可避免漏氣狀況發生，因此於800℃下最高功率密度為61mW/cm2，其性能相較於雙層該電解質薄膜之單電池明顯提升。當添加3wt%氧化鎳至該電解質粉末中，將有效提升該電解質薄膜燒結性質，使得該電解質薄膜層數可從三層減少至兩層，進而縮短離子傳輸距離，且避免連通孔洞所造成之漏氣狀況，因此，如圖13(c)所示，於800℃下所測得之最高功率密度為101mW/cm2，此能量密度高於其他未添加助燒結劑之單電池。 Single cell IV performance curve measurement and analysis: The single cell prepared by the spin coating method is packaged on the test bench, the anode end is filled with hydrogen at 20cc/min, and the nickel oxide of the anode is reduced to metallic Ni, and then 200cc is applied to the anode end. Pass hydrogen gas and 600cc/min air (21% N 2 +79% O 2 ) at the cathode end, and measure the battery performance at 800 ℃, 700 ℃, 600 ℃, and 550 ℃. As shown in Figure 13(a), it is a single cell with a double layer of the electrolyte film and uses La 0.6 Sr 0.4 Co 0.8 Fe 0.2 O 3 ( LSCF) as the cathode. The open circuit voltage (OCV) measured at 800°C is 0.35V , The voltage value is far from the theoretical value, which means that the electrolyte structure is not dense enough, and there are still pores, which causes the reaction gas to pass through the electrolyte. The maximum power density at 800 ℃ is 5.93mW/cm 2 , which is too low for the energy density. Low, if the electrolyte is improved, the battery performance will be effectively improved. In order to avoid the leakage of electrolyte caused by connecting holes in the electrolyte, the number of times of coating the electrolyte film was increased to three layers. Figure 13(b) shows a single cell with three layers of the electrolyte film and using LSCF as the cathode, measured at 800°C. The open circuit voltage (OCV) is 0.99V, which is close to the theoretical value ~1.0V, which means that the electrolyte is dense enough to avoid air leakage. Therefore, the maximum power density at 800℃ is 61mW/cm 2 , and its performance is compared to double-layer The single cell of the electrolyte film is significantly improved. When 3wt% nickel oxide is added to the electrolyte powder, the sintering properties of the electrolyte film will be effectively improved, so that the number of layers of the electrolyte film can be reduced from three to two, thereby shortening the ion transmission distance and avoiding leakage caused by connecting holes. Therefore, as shown in Figure 13(c), the highest power density measured at 800°C is 101mW/cm 2 , which is higher than other single cells without added sintering aid.
單電池之EIS測量與分析：本發明藉由電化學阻抗頻譜測量了解全電池內部損失之大小，並將各種損失作為改善電池性能之依據，圖14所示，為典型的Nyquist plot於不同溫度下之阻抗圖，掃描頻率範圍由105Hz至0.1Hz，由原點至實部高頻率掃描起始點間距屬於歐姆阻抗(Ohmic resistance,Ro)，由高頻率掃描至低頻率之間距屬於極化電阻(Polarization resistance,Rp)，並且Ro與Rp皆隨著溫度下降而上升，Ro主要原因來自於電子位於電極移動與離子於電解質中遷移時所受到之阻抗，Rp與反應氣體於電極表面進行電化學反應亦或是反應氣體供給相關。如圖14(a)所示，為三層該電解質薄膜全電池之阻抗圖，圖14(b) 為兩層加入3%氧化鎳的該電解質薄膜全電池之阻抗圖，當添加氧化鎳後該電解質薄膜可由三層減少至兩層，其質子傳輸距離縮短，且電解質結構更為緻密，減少質子傳輸之阻礙，因此Ro將有效降低，於800℃時，Ro由5.48Ωcm2降低至3.97Ωcm2，此外，由於電解質緻密性提升將使得電解質與陰、陽極有效反應面積將有所提升，因此於800℃，Rp由0.33Ωcm2降低至0.16Ωcm2。 EIS measurement and analysis of single cell: The present invention uses electrochemical impedance spectroscopy to measure the internal loss of the whole cell, and uses various losses as the basis for improving battery performance. Figure 14 shows a typical Nyquist plot at different temperatures. The impedance diagram, the scanning frequency range is from 10 5 Hz to 0.1 Hz, the distance from the origin to the real part of the high-frequency scanning starting point belongs to Ohmic resistance (R o ), and the distance from high-frequency scanning to low-frequency scanning belongs to extreme Polarization resistance (R p ), and both R o and R p increase as the temperature drops. The main reason for R o comes from the resistance of electrons moving in the electrode and migration of ions in the electrolyte. R p and reaction The electrochemical reaction of the gas on the electrode surface is also related to the supply of reactive gas. As shown in Figure 14(a), it is the impedance diagram of the three-layer electrolyte film full battery, and Figure 14(b) is the impedance diagram of the electrolyte film full battery with two layers of 3% nickel oxide. When nickel oxide is added, the Layer electrolyte membrane may be reduced to two, which proton transmission distance shorter, more compact structure and the electrolyte, reducing the obstruction of proton transport, thus effectively reducing the R o, while at 800 ℃, R o decreased from 3.97 to 5.48Ωcm 2 Ωcm 2, in addition, since the electrolyte is improved in density such that the cathode electrolyte, the anode active area of the reaction will be improved, so at 800 ℃, R p decreased from 0.33Ωcm 2 to 0.16Ωcm 2.
據此，本發明所提供之一種固態氧化物燃料電池之電解質製備方法，藉由添加氧化鎳，並配合旋轉塗佈技術製備之電解質薄膜，其可減少電解質出現孔洞與縫隙，藉此提升質子傳導效率。 Accordingly, the present invention provides a solid oxide fuel cell electrolyte preparation method. By adding nickel oxide and using an electrolyte membrane prepared by spin coating technology, it can reduce the presence of holes and gaps in the electrolyte, thereby improving proton conduction. effectiveness.
10:固態氧化物燃料電池之電解質製備方法 10: Preparation method of electrolyte for solid oxide fuel cell
20:旋轉盤 20: Rotating disc
30:電解質薄膜 30: Electrolyte film
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