TWI566460B - Method of making electrolyte of sofc by reduction of anode - Google Patents
Method of making electrolyte of sofc by reduction of anode Download PDFInfo
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- TWI566460B TWI566460B TW104142009A TW104142009A TWI566460B TW I566460 B TWI566460 B TW I566460B TW 104142009 A TW104142009 A TW 104142009A TW 104142009 A TW104142009 A TW 104142009A TW I566460 B TWI566460 B TW I566460B
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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
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- 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
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Description
本發明係有關於一種透過還原技術製造燃料電池電解質之方法，特別是指利用碳熱微波還原法將氧化鎳/氧化鋯陽極基材表面還原出具有金屬鎳的導電層，並可直接以該導電層作為電極，用以沉積氧化鋯粉體堆積層供作為製作電解質的方法。 The invention relates to a method for manufacturing a fuel cell electrolyte through a reduction technique, in particular to reducing a surface of a nickel oxide/zirconia anode substrate by a carbon thermal microwave reduction method to a conductive layer having metallic nickel, and directly using the conductive layer. The layer serves as an electrode for depositing a zirconia powder buildup layer as a method of making an electrolyte.
固體氧化物燃料電池(SOFC)的缺點在於氧化鋯電解質過厚，一般約為800微米，因此SOFC操作溫度需高達800℃至900℃左右，以提高氧離子擴散速度。然而，若能夠降低氧化鋯電解質厚度，將可使操作溫度降低，且縮短氧離子擴散距離。其中，純氧化鋯的效果不如加入氧化釔分散強化的氧化鋯。 A disadvantage of solid oxide fuel cells (SOFC) is that the zirconia electrolyte is too thick, typically about 800 microns, so the SOFC operating temperature needs to be as high as 800 ° C to 900 ° C to increase the oxygen ion diffusion rate. However, if the thickness of the zirconia electrolyte can be lowered, the operating temperature can be lowered and the oxygen ion diffusion distance can be shortened. Among them, the effect of pure zirconia is not as good as the addition of yttria dispersion-strengthened zirconia.
製作低於厚度100微米的氧化鋯電解質常見的方式是電泳沉積法，例如張詠策於中華民國99年所提出之「電泳沉積法製備固態氧化物燃料電池」。 A common way to make zirconia electrolytes with a thickness of less than 100 microns is by electrophoretic deposition. For example, Zhang Yiping proposed the "electrolytic deposition method for preparing solid oxide fuel cells" proposed by the Republic of China in 1999.
然而，習知SOFC的陽極為氧化鎳/氧化鋯，是一種陶瓷材料，電阻值大於1MΩ，導電性差，採用電泳沉積時需要在陽極上製作背電極提高沉積效果，藉以使電解質粉末可吸附沉積在陽極上，但是此種方式約需通入100伏特至300伏特的高電壓才能使電解質粉末穩定沉積在陽極上，若能使氧化鎳/氧 化鋯基材可導電，加在陽極的電壓降可以大幅降低，減少觸電危險，而且不需要在陽極上製作背電極，就有沉積效果。 However, the anode of the conventional SOFC is nickel oxide/zirconia, which is a ceramic material with a resistance value greater than 1 MΩ and poor conductivity. When electrophoretic deposition is used, it is necessary to form a back electrode on the anode to improve the deposition effect, so that the electrolyte powder can be adsorbed and deposited. On the anode, but this way requires about a high voltage of 100 volts to 300 volts to allow the electrolyte powder to be stably deposited on the anode, if it can make nickel oxide / oxygen The zirconium substrate can be electrically conductive, the voltage drop applied to the anode can be greatly reduced, the risk of electric shock is reduced, and the back electrode is not required to be formed on the anode, and deposition effect is obtained.
一般電泳液分為有機溶劑電泳液和水基電泳液，而能夠適應此種100伏特至300伏特下操作的電泳液僅有有機溶劑電泳液，但是有機溶劑電泳液操作時需控制溫度在0℃至5℃，以穩定沉積速度，並防止有機溶液因高溫揮發而改變成分，且有機溶劑電泳液的閃火點低，具高揮發性，在100伏特至300伏特下操作時，有***可能，對人體和公共安全有一定的危險性，另外在100伏特至300伏特下操作時，溶液受高電壓加熱，溫度會快速升溫，不利粉體電泳沈積在基材表面，沈積速度慢且堆疊密度低。也就是說，若能夠使基材更易導電，加在陽極的電壓降將可以大幅降低，有利於電泳安全性，沈積速度快且堆疊緻密，粉體堆疊密度愈高，就愈容易緻密燒結，能以更薄的電解質隔絕SOFC陰陽極兩端的氣體分子直接交流混合，卻同時能達到縮短氣體離子擴散路徑和薄化電解質的目的。 Generally, the electrophoresis liquid is divided into an organic solvent electrophoresis liquid and a water-based electrophoresis liquid, and the electrophoresis liquid capable of operating at such a pressure of 100 volts to 300 volts has only an organic solvent electrophoresis liquid, but the organic solvent electrophoresis liquid needs to be controlled at a temperature of 0 ° C. Up to 5 ° C, to stabilize the deposition rate, and to prevent the organic solution from changing components due to high temperature volatilization, and the organic solvent electrophoresis liquid has a low flash point and high volatility. When operating at 100 volts to 300 volts, there is an explosion possibility. It is dangerous to the human body and public safety. In addition, when operating at 100 volts to 300 volts, the solution is heated by high voltage, the temperature will rise rapidly, and the powder is electrophoretically deposited on the surface of the substrate, and the deposition speed is slow and the stacking density is low. . That is to say, if the substrate can be made more conductive, the voltage drop applied to the anode can be greatly reduced, which is beneficial to the safety of electrophoresis, the deposition speed is fast and the stack is dense, and the higher the powder stack density, the easier the dense sintering is. The thinner electrolyte is used to isolate the gas molecules at both ends of the SOFC anode and cathode, and the gas molecules are directly exchanged and mixed, but at the same time, the gas ion diffusion path and the thinning electrolyte are shortened.
水基電泳液較安全且可在室溫下操作，但是採用水基電泳液，當工作電壓高於1.67伏特時，水基電泳液會產生電解水的現象而分解出氣體，氣泡在待沈積表面生成和成長，其成長和上浮過程都會干擾電解質粉末在陽極上的排列方式，使其粉體堆疊密度降低及均勻度不佳，影響SOFC陰陽極兩端的透氣性。傳統作法在工作電壓低於1.67伏特時，由於試片厚度遠大於1.67伏特在液體中產生的電雙層(double layer)厚度，試片表面不會有粉體被吸引而沈積，也就是說，傳統作法無法在工作電壓低於1.67伏特時沈積粉體。 Water-based electrophoresis liquid is safer and can be operated at room temperature, but with water-based electrophoresis liquid, when the working voltage is higher than 1.67 volts, the water-based electrophoresis liquid will produce electrolyzed water to decompose the gas, and the bubbles are on the surface to be deposited. When it is formed and grown, its growth and floating process will interfere with the arrangement of the electrolyte powder on the anode, which will reduce the density of the powder stack and the poor uniformity, which will affect the gas permeability of the cathode and cathode of the SOFC. Conventionally, when the operating voltage is lower than 1.67 volts, since the thickness of the test piece is much larger than the thickness of the double layer produced in the liquid at 1.67 volts, no powder is attracted and deposited on the surface of the test piece, that is, Traditionally, it is not possible to deposit powder at operating voltages below 1.67 volts.
為了解決此問題，本發明不採用背電極，而是利用碳熱微波還原方式在氧化鎳/氧化鋯陽極基材表面還原出金屬鎳，當足夠的金屬鎳形成一鎳/氧化鋯導電層，此導電金屬鎳就能作為電泳沉積製程的電極，而由於不使用背電極，因此電泳沉積製程所通入的電壓可低於1.67伏特，也因此可使用安全性高的水基電泳液，對燃料電池而言，後續電解質和陰極的燒結都在氧化氣氛下進行，鎳/氧化鋯仍會氧化成氧化鎳/氧化鋯。而單純鍍上一層鎳層，雖然亦可解決導電問題，但此鎳層會在後續電解質和陰極燒結的氧化氣氛下形成氧化鎳層，等於變相在燃料電池陽極和電解質之間加入氧化鎳層，而非氧化鎳/氧化鋯陽極基材直接鄰接氧化鋯電解質，因此單純鍍上一層鎳層並不可行。 In order to solve this problem, the present invention does not use a back electrode, but uses a carbon thermal microwave reduction method to reduce metallic nickel on the surface of the nickel oxide/zirconia anode substrate, and when sufficient metal nickel forms a nickel/zirconia conductive layer, The conductive metal nickel can be used as an electrode for the electrophoretic deposition process, and since the back electrode is not used, the voltage applied to the electrophoretic deposition process can be lower than 1.67 volts, so that a highly safe water-based electrophoresis liquid can be used for the fuel cell. In contrast, the subsequent sintering of the electrolyte and the cathode are carried out under an oxidizing atmosphere, and the nickel/zirconia is still oxidized to nickel oxide/zirconia. Simply plating a layer of nickel, although it can also solve the problem of conduction, the nickel layer will form a nickel oxide layer under the oxidizing atmosphere of subsequent electrolyte and cathode sintering, which is equivalent to adding a nickel oxide layer between the anode of the fuel cell and the electrolyte. The non-nickel oxide/zirconia anode substrate is directly adjacent to the zirconia electrolyte, so simply plating a layer of nickel is not feasible.
另外，由於純氧化鋯的效果不如加入氧化釔穩定化的氧化鋯，但習慣上亦簡稱加入氧化釔的氧化鋯為氧化鋯，先予述明。 Further, since the effect of pure zirconia is not as good as that of yttria-stabilized zirconia, it is conventionally referred to as zirconia added as zirconia, which will be described first.
本發明係一種透過還原技術製造燃料電池電解質之方法，包括：A.在一氧化鎳/氧化鋯陽極基材上施加一微波，並以碳作為還原劑，使該氧化鎳/氧化鋯陽極基材進行還原反應，至少在該氧化鎳/氧化鋯陽極基材表面形成含有金屬鎳之一導電層；B.在該導電層上沉積一氧化鋯粉體堆積層，該氧化鋯粉體堆積層即為氧化鋯電解質。 The invention relates to a method for manufacturing a fuel cell electrolyte through a reduction technique, comprising: A. applying a microwave on a nickel oxide/zirconia anode substrate and using carbon as a reducing agent to make the nickel oxide/zirconia anode substrate Performing a reduction reaction to form at least one conductive layer containing metallic nickel on the surface of the nickel oxide/zirconia anode substrate; B. depositing a zirconium oxide powder buildup layer on the conductive layer, the zirconia powder deposited layer is Zirconia electrolyte.
進一步，步驟A的氧化鎳/氧化鋯陽極基材的還原程度係使該導電層的電阻值不大於22毫歐姆。 Further, the degree of reduction of the nickel oxide/zirconia anode substrate of step A is such that the electrical resistance of the conductive layer is not more than 22 milliohms.
進一步，當該氧化鎳/氧化鋯陽極基材生坯密度介於3.1g/mm3至3.45g/mm3時，該微波之單位立方厘米的功率介於0.16瓦至6.37瓦，還原時間不超過12分鐘。 Further, when the nickel oxide/zirconia anode substrate has a green density of from 3.1 g/mm3 to 3.45 g/mm3, the power of the microwave unit centimeter is between 0.16 watts and 6.37 watts, and the reduction time is no more than 12 minutes. .
進一步，當該氧化鎳/氧化鋯陽極基材為錠狀，且直徑介於10厘米至20厘米，厚度介於2厘米至3厘米，密度介於3.1g/mm3至3.45g/mm3時，該微波之功率介於150瓦至1000瓦，還原時間不超過12分鐘。較佳的是，該微波之功率介於500瓦至700瓦，還原時間介於6分鐘至12分鐘。 Further, when the nickel oxide/zirconia anode substrate is in the form of an ingot and has a diameter of 10 cm to 20 cm, a thickness of 2 cm to 3 cm, and a density of 3.1 g/mm 3 to 3.45 g/mm 3 , The power of the microwave is between 150 watts and 1000 watts, and the reduction time is no more than 12 minutes. Preferably, the power of the microwave is between 500 watts and 700 watts and the reduction time is between 6 minutes and 12 minutes.
進一步，步驟A的還原反應的溫度範圍介於650度C至850度C。 Further, the temperature of the reduction reaction of the step A ranges from 650 ° C to 850 ° C.
進一步，作為還原劑的碳與氧化鎳/氧化鋯陽極基材相接觸，加速接觸區的反應速度，此接觸區可定義為碳擇區。 Further, the carbon as a reducing agent is brought into contact with the nickel oxide/zirconia anode substrate to accelerate the reaction rate of the contact zone, and the contact zone can be defined as a carbon selective zone.
進一步，步驟B的沉積製程採用電泳沉積製程。 Further, the deposition process of step B uses an electrophoretic deposition process.
透過上述技術特徵可產生下列功效： Through the above technical features, the following effects can be produced:
1.使用碳熱微波還原法可在氧化鎳/氧化鋯陽極基材表面還原出具有面分佈的金屬鎳導電層，其平均電阻值約為22毫歐姆。因此可採用水基電泳液進行低電壓電泳沉積製程，無須採用有機溶劑和高電壓，更安全和容易操作，不需冷卻溶液的控溫設計，恰能利用低電壓製作氧化鋯薄膜(氧化鋯電解質)，低電壓和無氣體擾動的特性，有助於粉體有序堆積而緻密化，且低電壓限制其可吸附的粉體層厚度，所得高緻密的薄層恰符合燃料電池使用。 1. Using a carbon thermal microwave reduction method, a metallic nickel conductive layer having a surface distribution can be reduced on the surface of the nickel oxide/zirconia anode substrate, and the average resistance value is about 22 milliohms. Therefore, the water-based electrophoresis liquid can be used for the low-voltage electrophoretic deposition process, without using an organic solvent and a high voltage, which is safer and easier to operate, does not require the temperature control design of the cooling solution, and can be used to fabricate a zirconia film (zirconia electrolyte) with a low voltage. The characteristics of low voltage and no gas perturbation contribute to the orderly packing of the powder and densification, and the low voltage limits the thickness of the powder layer which can be adsorbed, and the resulting highly dense thin layer conforms to the use of the fuel cell.
2.由於碳和一氧化鎳都可以吸收微波而受熱，此種設計有利於減少快速升溫過程的熱衝擊，相對減少成品缺陷，例如裂縫，另外碳還可以燃燒提供大量氧化熱，使基材與碳粉靠近處的還原效果更快，而使微波碳熱有擇區還原效果，且作為還原劑的碳與氧化鎳/氧化鋯陽極基材相接觸，其燃燒熱加速接觸區的反應速度，可利用碳擇區設定試片需要反應的部位。 2. Since both carbon and nickel monoxide can absorb microwaves and be heated, this design is beneficial to reduce the thermal shock of the rapid heating process, relatively reducing the defects of the finished product, such as cracks, and the carbon can also burn to provide a large amount of heat of oxidation, so that the substrate and the substrate The reduction effect of the carbon powder is faster, and the microwave carbon heat selective reduction effect, and the carbon as the reducing agent is in contact with the nickel oxide/zirconia anode substrate, and the combustion heat accelerates the reaction speed of the contact zone. The carbon selection zone is used to set the site where the test piece needs to be reacted.
3.使用碳熱微波還原法進行還原時，因為加熱速度快，所形成之導電層的金屬鎳晶粒較傳統加溫方式所得的小，晶粒細小可產生較多晶界，可 增加燃料電池運作過程中更多氫離子擴散路徑，同樣的工作溫度與壓力下可供給較多的反應氫，且鎳可作為觸媒，直接對輕油等碳氫化合物作觸媒催化反應取得氫氣，晶粒的細小化可提高催化反應效果使SOFC效率提升，且增加可使用燃料的多樣性，如天然氣、甲醇、石油、煤碳等。 3. When using carbon thermal microwave reduction method for reduction, because the heating speed is fast, the metal nickel crystal grains of the formed conductive layer are smaller than those obtained by the conventional heating method, and the crystal grains are fine to generate more grain boundaries. Increasing the hydrogen ion diffusion path during the operation of the fuel cell, the same working temperature and pressure can supply more reaction hydrogen, and nickel can be used as a catalyst to directly react with hydrocarbons such as light oil to obtain hydrogen. The grain size reduction can improve the catalytic reaction effect and increase the SOFC efficiency, and increase the diversity of available fuels, such as natural gas, methanol, petroleum, coal and the like.
4.此導電層可作為電泳沈積氧化鋯粉體所需的電極。 4. This conductive layer can be used as an electrode for electrophoretic deposition of zirconia powder.
5.此導電層在後續燒結過程中，該導電層具有與氧化鎳/氧化鋯陽極基材與該氧化鋯電解質近似的組成，提供作為氧化鎳/氧化鋯和氧化鋯乾燥收縮和燒結收縮的應力緩衝層，避免兩者間的界面產生裂痕或是氧化鋯層裂開。 5. The conductive layer has a composition similar to that of the nickel oxide/zirconia anode substrate and the zirconia electrolyte during subsequent sintering, providing stress as dry shrinkage and sintering shrinkage of nickel oxide/zirconia and zirconia The buffer layer prevents cracks in the interface between the two or the zirconia layer is cracked.
(1)‧‧‧氧化鎳陽極基材 (1)‧‧‧ Nickel oxide anode substrate
(11)‧‧‧導電層 (11) ‧‧‧ Conductive layer
(2)‧‧‧氧化鋯電解質 (2) ‧ ‧ zirconia electrolyte
(3)‧‧‧金屬鎳陽極基材 (3)‧‧‧Metal nickel anode substrate
[第一圖]係為本發明實施例中，電解質成形方法的流程圖。 [First Diagram] is a flow chart of an electrolyte forming method in an embodiment of the present invention.
[第二A圖]係為本發明實施例中，碳熱微波還原法在氧化鎳/氧化鋯陽極基材上所形成之導電層的微結構顯微圖。 [Fig. 2A] is a microscopic micrograph of a conductive layer formed on a nickel oxide/zirconia anode substrate by a carbon thermal microwave reduction method in an embodiment of the present invention.
[第二B圖]係為本發明實施例中，電爐碳熱還原法在氧化鎳/氧化鋯陽極基材上所形成之導電層的微結構顯微圖。 [Fig. 2B] is a micrograph of a microstructure of a conductive layer formed on a nickel oxide/zirconia anode substrate by an electric furnace carbothermal reduction method in an embodiment of the present invention.
[第三A圖]係為本發明實施例中，碳熱微波還原法在氧化鎳/氧化鋯陽極基材上所形成之導電層的金屬鎳分佈顯微圖。 [Third A] is a microscopic view of the distribution of metallic nickel of the conductive layer formed on the nickel oxide/zirconia anode substrate by the carbon thermal microwave reduction method in the embodiment of the present invention.
[第三B圖]係為本發明實施例中，碳熱微波還原法在氧化鎳/氧化鋯陽極基材上所形成之導電層的金屬鎳分佈的EDS圖譜。 [Third B] is an EDS spectrum of the metallic nickel distribution of the conductive layer formed on the nickel oxide/zirconia anode substrate by the carbon thermal microwave reduction method in the examples of the present invention.
[第四A圖]係為本發明實施例中，電爐碳熱還原法在氧化鎳/氧化鋯陽極基材上所形成之導電層的金屬鎳分佈顯微圖。 [Fourth A] is a microscopic view of the distribution of metallic nickel of a conductive layer formed on a nickel oxide/zirconia anode substrate by an electric furnace carbothermal reduction method in an embodiment of the present invention.
[第四B圖]係為本發明實施例中，電爐碳熱還原法在氧化鎳/氧化鋯陽極基材上所形成之導電層的金屬鎳分佈的EDS圖譜。 [Fourth B] is an EDS spectrum of the metallic nickel distribution of the conductive layer formed on the nickel oxide/zirconia anode substrate by the electric furnace carbothermal reduction method in the embodiment of the present invention.
[第五A圖]係為本發明實施例中，以電壓1伏特進行電泳沉積氧化鋯電解質時，表面暗區分佈圖。 [Fig. 5A] is a distribution diagram of the dark area of the surface when the zirconia electrolyte is electrophoretically deposited at a voltage of 1 volt in the embodiment of the present invention.
[第五B圖]係為本發明實施例中，以電壓2伏特進行電泳沉積氧化鋯電解質時，表面暗區分佈圖。 [Fig. 5B] is a distribution diagram of the dark area of the surface when the zirconia electrolyte is electrophoretically deposited at a voltage of 2 volts in the embodiment of the present invention.
[第五C圖]係為本發明實施例中，以電壓3伏特進行電泳沉積氧化鋯電解質時，表面暗區分佈圖。 [Fifth C] is a distribution diagram of the dark area of the surface when the zirconia electrolyte is electrophoretically deposited at a voltage of 3 volts in the embodiment of the present invention.
[第五D圖]係為本發明實施例中，以電壓4伏特進行電泳沉積氧化鋯電解質時，表面暗區分佈圖。 [Fifth D] is a distribution diagram of the dark area of the surface when the zirconia electrolyte is electrophoretically deposited at a voltage of 4 volts in the embodiment of the present invention.
[第六A圖]係為本發明實施例中，以電壓1.5伏特進行電泳沉積氧化鋯電解質的顯微圖。 [Sixth A] is a micrograph of electrophoretic deposition of a zirconia electrolyte at a voltage of 1.5 volts in the embodiment of the present invention.
[第六B圖]係為本發明實施例中，以電壓1.7伏特進行電泳沉積氧化鋯電解質的顯微圖。 [Sixth B] is a micrograph of electrophoretic deposition of a zirconia electrolyte at a voltage of 1.7 volts in the embodiment of the present invention.
[第七A圖]係為本發明實施例中，以電壓1伏特進行電泳沉積氧化鋯電解質，沉積時間36秒的表面暗區分佈圖。 [Seventh A] is a surface dark area distribution map in which the zirconia electrolyte is electrophoretically deposited at a voltage of 1 volt for a deposition time of 36 seconds in the embodiment of the present invention.
[第七B圖]係為本發明實施例中，以電壓1伏特進行電泳沉積氧化鋯電解質，沉積時間72秒的表面暗區分佈圖。 [Fig. 7B] is a surface dark area distribution map in which an zirconia electrolyte is electrophoretically deposited at a voltage of 1 volt for a deposition time of 72 seconds in the embodiment of the present invention.
[第七C圖]係為本發明實施例中，以電壓1伏特進行電泳沉積氧化鋯電解質，沉積時間108秒的表面暗區分佈圖。 [Seventh C] is a surface dark area distribution map in which a zirconia electrolyte is electrophoretically deposited at a voltage of 1 volt and a deposition time of 108 seconds is used in the embodiment of the present invention.
[第七D圖]係為本發明實施例中，以電壓1伏特進行電泳沉積氧化鋯電解質，沉積時間144秒的表面暗區分佈圖。 [Seventh D] is a surface dark area distribution map in which the zirconia electrolyte is electrophoretically deposited at a voltage of 1 volt for a deposition time of 144 seconds in the embodiment of the present invention.
[第七E圖]係為本發明實施例中，以電壓1伏特進行電泳沉積氧化鋯電解質，沉積時間180秒的表面暗區分佈圖。 [Seventh E] is a surface dark area distribution map in which the zirconia electrolyte is electrophoretically deposited at a voltage of 1 volt for a deposition time of 180 seconds.
[第八圖]係為本發明實施例中，以電壓1伏特進行電泳沉積氧化鋯電解質時，電流的變化圖。 [Eighth image] is a graph showing changes in current when electrophoretic deposition of a zirconia electrolyte at a voltage of 1 volt is used in the embodiment of the present invention.
[第九圖]係為本發明實施例中，以PMI量測持續升壓至60psi，通孔直徑分佈圖。 [Ninth aspect] is a through-hole diameter distribution diagram in which the PMI is continuously boosted to 60 psi in the embodiment of the present invention.
[第十圖]係為本發明實施例中，該導電層具有與氧化鎳/氧化鋯陽極基材與該氧化鋯電解質近似的組成，可作為氧化鎳/氧化鋯和氧化鋯乾燥收縮和燒結收縮的應力緩衝層，避免兩者間的界面產生裂痕的顯微圖。 [Tenth Graph] In the embodiment of the present invention, the conductive layer has a composition similar to that of the nickel oxide/zirconia anode substrate and the zirconia electrolyte, and can be used as a dry shrinkage and sintering shrinkage of nickel oxide/zirconia and zirconia. The stress buffer layer avoids micrographs of cracks at the interface between the two.
綜合上述技術特徵，本發明透過還原技術製造燃料電池電解質之方法的主要功效將可於下述實施例清楚呈現。 In summary of the above technical features, the main effects of the method of the present invention for producing a fuel cell electrolyte by a reduction technique will be apparent from the following examples.
參閱第一圖所示，本實施例包括： Referring to the first figure, this embodiment includes:
A.在一氧化鎳/氧化鋯陽極基材(1)上進行還原反應，至少在該氧化鎳/氧化鋯陽極基材(1)表面形成含有金屬鎳之一導電層(11)，本實施例中，所述還原反應使用碳熱微波還原法，係在該氧化鎳/氧化鋯陽極基材(1)上施加一微波，並以碳作為還原劑，使該氧化鎳/氧化鋯陽極基材(1)進行還原反應，還原反應的溫度範圍介於650度C至850度C，而該氧化鎳/氧化鋯陽極基材(1)之氧化鋯採用3YSZ(3Y2O3-ZrO2)。其中，該氧化鎳/氧化鋯陽極基材(1)的還原程度係使該導電層(11)的電阻值不大於22毫歐姆。 A. a reduction reaction on the nickel oxide/zirconia anode substrate (1), forming at least one conductive layer (11) containing metallic nickel on the surface of the nickel oxide/zirconia anode substrate (1), this embodiment The reduction reaction uses a carbon thermal microwave reduction method in which a microwave is applied to the nickel oxide/zirconia anode substrate (1), and the nickel oxide/zirconia anode substrate is made of carbon as a reducing agent ( 1) The reduction reaction is carried out at a temperature ranging from 650 ° C to 850 ° C, and the zirconia of the nickel oxide/zirconia anode substrate (1) is 3YSZ (3Y2O3-ZrO 2 ). Wherein, the degree of reduction of the nickel oxide/zirconia anode substrate (1) is such that the electric resistance of the conductive layer (11) is not more than 22 milliohms.
B.以電泳沉積製程在該導電層(11)上沉積一氧化鋯粉體堆積層，該氧化鋯粉體堆積層即為氧化鋯電解質(2)，該氧化鋯電解質(2)採用8YSZ(8Y2O3-ZrO2)，其中，電泳沉積製程使用水基電泳液，且製程電壓不高於1.67伏特。 B. depositing a zirconium oxide powder buildup layer on the conductive layer (11) by an electrophoretic deposition process, the zirconia powder buildup layer being a zirconia electrolyte (2), and the zirconia electrolyte (2) adopting 8YSZ (8Y2O3) -ZrO2), wherein the electrophoretic deposition process uses a water-based electrophoresis solution and the process voltage is not higher than 1.67 volts.
C.將該氧化鎳/氧化鋯陽極基材(1)與該氧化鋯電解質(2)進行共燒結，且共燒結的方式採用電爐共燒。 C. The nickel oxide/zirconia anode substrate (1) is co-sintered with the zirconia electrolyte (2), and co-sintering is carried out by electric furnace co-firing.
D.將共燒結後之該氧化鎳/氧化鋯陽極基材(1)與該氧化鋯電解質(2)進行還原，使該氧化鎳/氧化鋯陽極基材(1)中的氧化鎳還原成金屬鎳而成為金屬鎳陽極基材(3)，且還原方式採用電爐碳熱還原法。之後，該氧化鋯電解質(2)即可再與陰極結合，成為固態氧化物燃料電池。 D. The co-sintered nickel oxide/zirconia anode substrate (1) and the zirconia electrolyte (2) are reduced to reduce nickel oxide in the nickel oxide/zirconia anode substrate (1) to metal Nickel is used as the metal nickel anode substrate (3), and the reduction method is an electric furnace carbothermal reduction method. Thereafter, the zirconia electrolyte (2) can be combined with the cathode to become a solid oxide fuel cell.
本實施例之實驗方式係先製作該氧化鎳/氧化鋯陽極基材：準備3YSZ、8YSZ、NiO、C粉末，粒徑分別介於0.1~0.5μm、0.04~0.1μm、1~10μm和1000~1300μm。先將NiO和3YSZ粉體以7：3的重量比例，另加入3wt%的PVA和適量鋯球(近瓶身高度一半)，再倒入酒精淹過粉體達瓶身的九分滿，置於250ml的PP密封塑膠罐內，以球磨機旋轉混合12小時，進行濕式混合，後取出乾燥，再過篩200mesh的篩網。再利用單軸乾壓，施加壓力約為250~300kg/cm2，製作該氧化鎳/氧化鋯陽極基材的生胚，尺寸為直徑16mm、厚度2.5mm，其生坯密度為3.10~3.45g/mm3。之後進行脫脂與鍛燒程序，其中PVA脫脂溫度為350℃，升溫速率為3℃/min，持溫一小時，煅燒參數以5℃/min的升溫速率繼續至800℃，並持溫一小時，達到適當的機械強度，而完成該氧化鎳/氧化鋯陽極基材的製作。 The experimental method of this embodiment is to first prepare the nickel oxide/zirconia anode substrate: prepare 3YSZ, 8YSZ, NiO, C powder, and the particle diameters are respectively 0.1~0.5μm, 0.04~0.1μm, 1~10μm and 1000~ 1300 μm. First, add NiO and 3YSZ powder in a weight ratio of 7:3, add 3wt% PVA and appropriate amount of zirconium ball (half the height of the bottle), then pour the alcohol into the powder to reach the bottle full of nine points. In a 250 ml PP sealed plastic can, it was rotated and mixed for 12 hours in a ball mill, wet-mixed, taken out and dried, and sieved through a 200 mesh screen. The uniaxial dry pressure is applied, and the pressure is about 250-300 kg/cm2, and the green embryo of the nickel oxide/zirconia anode substrate is prepared to have a diameter of 16 mm and a thickness of 2.5 mm, and the green density is 3.10 to 3.45 g/ Mm3. Then, the degreasing and calcining process is carried out, wherein the PVA degreasing temperature is 350 ° C, the heating rate is 3 ° C / min, the temperature is maintained for one hour, the calcination parameter is continued to 800 ° C at a heating rate of 5 ° C / min, and the temperature is maintained for one hour. The formation of the nickel oxide/zirconia anode substrate is completed by achieving appropriate mechanical strength.
上述尺寸的氧化鎳/氧化鋯陽極基材，其碳熱微波還原法之微波功率介於150瓦至1000瓦，較佳是500瓦至700瓦，更詳細的說，該微波之單位立方厘米的功率介於0.16瓦至6.37瓦，還原時間不超過12分鐘，上述尺寸約為6~12分鐘，其中，作為還原劑的碳與氧化鎳/氧化鋯陽極基材相接觸，碳升溫速度比氧化鎳/氧化鋯陽極基材快，可藉傳導加速接觸區的反應速度，使氧化鎳/ 氧化鋯陽極基材與碳粉靠近處的還原效果更快，而使微波碳熱有擇區還原效果。 The nickel oxide/zirconia anode substrate of the above size has a microwave power of a microwave thermal microwave reduction method of from 150 watts to 1000 watts, preferably from 500 watts to 700 watts, and more specifically, the unit of the microwave is cubic centimeters. The power is between 0.16 watts and 6.37 watts, the reduction time is no more than 12 minutes, and the above size is about 6 to 12 minutes. Among them, the carbon as a reducing agent is in contact with the nickel oxide/zirconia anode substrate, and the carbon heating rate is higher than that of nickel oxide. /Zirconium oxide anode substrate is fast, can accelerate the reaction rate of the contact zone by conduction, so that nickel oxide / The reduction effect of the zirconia anode substrate and the carbon powder is faster, and the microwave carbon heat has a selective reduction effect.
再製作水基電泳液，其中，水基電泳液之氧化鋯粉體的濃度為濃度10g/L。本實驗係量取240g的水和2.4g氨水，以超音波震盪使溶液均勻混合，再加入分散劑(Darvan C)及氧化鋯粉末(8YSZ)，比例是5：100，續以超音波震盪一小時，使8YSZ粉末均勻分散於懸浮溶液中。 Further, a water-based electrophoresis liquid is prepared, wherein the concentration of the zirconia powder of the water-based electrophoresis liquid is 10 g/L. In this experiment, 240 g of water and 2.4 g of ammonia water were weighed, and the solution was uniformly mixed by ultrasonic vibration, and then a dispersant (Darvan C) and zirconia powder (8YSZ) were added, the ratio was 5:100, and the ultrasonic wave was oscillated. In an hour, the 8YSZ powder was uniformly dispersed in the suspension solution.
之後進行電泳沉積製程，將氧化鋯電解質沉積在該氧化鎳/氧化鋯陽極基材的導電層，電泳沉積製程的溫度介於25℃至30℃，製程時間介於36秒至180秒。 Thereafter, an electrophoretic deposition process is performed to deposit a zirconia electrolyte on the conductive layer of the nickel oxide/zirconia anode substrate. The electrophoretic deposition process has a temperature between 25 ° C and 30 ° C and a process time of between 36 seconds and 180 seconds.
參閱第二A圖及第二B圖所示，比較電爐碳熱還原法與本發明之碳熱微波還原法在氧化鎳/氧化鋯陽極基材上所形成之導電層的晶粒大小。其中，本發明之碳熱微波還原法所形成之導電層的晶粒較小，晶粒細小可產生較多晶界，可增加更多氫離子擴散路徑，同樣的溫度與壓力下可供給較多的反應氫，且鎳可作為觸媒，直接對輕油等碳氫化合物作觸媒催化反應取得氫氣，晶粒的細小化可提高催化反應效果使SOFC效率提升，且增加可使用燃料的多樣性，如天然氣、甲醇、石油、煤碳等。 Referring to Figures 2A and 2B, the grain size of the conductive layer formed on the nickel oxide/zirconia anode substrate of the electric furnace carbothermal reduction method and the carbon thermal microwave reduction method of the present invention is compared. Wherein, the conductive layer formed by the carbon thermal microwave reduction method of the invention has small crystal grains, and the fine crystal grains can generate more grain boundaries, which can increase more hydrogen ion diffusion paths, and can supply more under the same temperature and pressure. Reactive hydrogen, and nickel can be used as a catalyst to directly react hydrogen with hydrocarbons such as light oil to obtain hydrogen. The finening of crystal grains can improve the catalytic reaction effect and improve the efficiency of SOFC, and increase the diversity of available fuels. Such as natural gas, methanol, petroleum, coal and so on.
再比較電爐碳熱還原法與本發明之碳熱微波還原法在氧化鎳/氧化鋯陽極基材上所形成之導電層的電阻值。其中，電爐碳熱還原法所形成之導電層的電阻值超過2M歐姆，在電泳沉積製程中幾乎無法導電，無法使用水基電泳液進行電泳沉積；然而本發明之碳熱微波還原法在氧化鎳/氧化鋯陽極基材上所形成之導電層的電阻值平均約為22毫歐姆。參閱第三A圖、第三B圖、第四A圖、第四B圖所示，使用電爐碳熱還原法與本發明之碳熱微波還原法所形成之 導電層的電阻值差異具大的原因在於：電爐碳熱還原法所形成之導電層的金屬鎳為點分佈，點之間彼此並不連續，而無法形成面分佈，因此無法形成連續的導電平面，以致於其電阻值大於2M歐姆。 The resistance values of the conductive layer formed on the nickel oxide/zirconia anode substrate by the carbon-thermal reduction method of the electric furnace and the carbon thermal microwave reduction method of the present invention are compared. Wherein, the electric resistance layer formed by the electric furnace carbon thermal reduction method has a resistance value exceeding 2 M ohm, and is hardly conductive in the electrophoretic deposition process, and cannot be electrophoretically deposited using a water-based electrophoresis liquid; however, the carbon thermal microwave reduction method of the present invention is in the nickel oxide The conductive layer formed on the zirconia anode substrate has an average resistance of about 22 milliohms. Referring to the third A diagram, the third B diagram, the fourth A diagram, and the fourth B diagram, the electric furnace carbon thermal reduction method and the carbon thermal microwave reduction method of the present invention are used. The reason why the difference in the resistance value of the conductive layer is large is that the metal nickel of the conductive layer formed by the carbon-thermal reduction method of the electric furnace is a point distribution, and the points are not continuous with each other, and the surface distribution cannot be formed, so that a continuous conductive plane cannot be formed. So that its resistance value is greater than 2M ohms.
由前述實驗得知，採用電爐碳熱還原法之導電層不論在晶粒大小及電阻值大小上皆不利於使用水基電泳液進行電泳沉積製程。再繼續參閱後續實驗將可發現本發明之碳熱微波還原法所製成之導電層極為適合使用水基電泳液進行電泳沉積氧化鋯電解質。 It is known from the foregoing experiments that the conductive layer using the electric furnace carbon thermal reduction method is disadvantageous in the electrophoretic deposition process using the water-based electrophoresis liquid regardless of the grain size and the resistance value. Further, referring to the subsequent experiments, it can be found that the conductive layer made by the carbon thermal microwave reduction method of the present invention is extremely suitable for electrophoretic deposition of a zirconia electrolyte using a water-based electrophoresis liquid.
參閱第五A圖至第五D圖所示，將該氧化鎳/氧化鋯陽極基材使用微波能量500W，微波時間30秒進行碳熱還原，再於所形成之導電層分別以1伏特至4伏特電壓值進行電泳沉積氧化鋯電解質，沉積時間60秒，由圖式中看出，當電泳沉積的電壓越大，氧化鋯電解質上的裂痕在圖上形成暗區，且暗區比例越大，圖上表面暗區是粉體間隙；再參閱第六A圖及第六B圖，分別是以電壓1.5伏特及1.7伏特進行電泳沉積氧化鋯電解質，其中以電壓1.7伏特進行電泳沉積時，有沉積不良而產生裂紋的情形。前述實驗說明了，當電泳電壓大於1.67伏特時水開始分解，陽極表面產生氣體，一般情形下是氧氣，氣體長成氣泡離開陽極表面，與氧化鋯粉體移動方向抵觸，擾動沉積界面，使電泳時氧化鋯粉體顆粒無序排列沉積，氣體在氧化鋯粉體表面產生，同時增加氧化鋯粉體間距離，減弱結合力，氧化鋯粉體無法緻密堆積，而提高功率導致過快的沉積行為，會使氧化鋯粉體沒有足夠的時間形成緻密堆積。參閱第七A圖至第七E圖所示，基於上述原因，以電壓1伏特進行電泳沉積氧化鋯電解質，沉積時間分別為36秒、72秒、108秒、144秒、180秒，再以1350℃進行共燒結後，發現電泳沉積 時間越長，則暗區分佈越少。根據上述說明得知，本發明採用水基電泳液進行電泳沉積時，電壓不得高於1.67伏特。 Referring to FIGS. 5A to 5D, the nickel oxide/zirconia anode substrate is subjected to carbothermal reduction using a microwave energy of 500 W for 30 seconds, and then the conductive layer is formed at 1 volt to 4 volts. The voltamer voltage was electrophoretically deposited with zirconia electrolyte for a deposition time of 60 seconds. As shown in the figure, when the electrophoretic deposition voltage is larger, the crack on the zirconia electrolyte forms a dark region on the graph, and the dark region ratio is larger. The dark area on the upper surface of the figure is the powder gap; refer to the sixth and sixth diagrams, respectively, electrophoretic deposition of zirconia electrolyte at a voltage of 1.5 volts and 1.7 volts, respectively, where the deposition is performed by electrophoretic deposition at a voltage of 1.7 volts. Poor and cracking. The foregoing experiment shows that when the electrophoresis voltage is greater than 1.67 volts, the water begins to decompose, and the surface of the anode generates gas. Under normal circumstances, oxygen is generated. The gas grows into bubbles and leaves the surface of the anode, which is in conflict with the movement direction of the zirconia powder, disturbing the deposition interface, and electrophoresis. When the zirconia powder particles are randomly arranged and deposited, the gas is generated on the surface of the zirconia powder, and the distance between the zirconia powders is increased, the bonding force is weakened, the zirconia powder cannot be densely packed, and the power is increased to cause excessive deposition behavior. This will leave the zirconia powder with insufficient time to form a dense buildup. Referring to the seventh to seventh E diagrams, for the above reasons, the zirconia electrolyte is electrophoretically deposited at a voltage of 1 volt, and the deposition time is 36 seconds, 72 seconds, 108 seconds, 144 seconds, 180 seconds, respectively, and then 1350. After co-sintering at °C, electrophoretic deposition was found The longer the time, the less the dark area is distributed. According to the above description, when the present invention uses an aqueous electrophoresis liquid for electrophoretic deposition, the voltage should not be higher than 1.67 volts.
參閱第八圖所示，係將該氧化鎳/氧化鋯陽極基材使用微波能量500W，微波時間30秒進行碳熱還原，還原反應的溫度範圍為650度C至850度C，再於所形成之導電層以1伏特進行電泳沉積氧化鋯電解質時，電流的變化。由圖中看出，當電泳沉積時間到達約150秒時，電流即無明顯變化。故本發明採用之電泳沉積時間介於5秒至200秒。而以電壓1伏特進行電泳沉積氧化鋯電解質，沉積時間分別為36秒、72秒、108秒、144秒、180秒，再以1350℃進行共燒結後，其厚度分別為3.08微米、5.29微米、6.18微米、7.239微米、11.38微米。 Referring to the eighth figure, the nickel oxide/zirconia anode substrate is subjected to carbothermal reduction using a microwave energy of 500 W and a microwave time of 30 seconds. The temperature of the reduction reaction ranges from 650 ° C to 850 ° C, and is formed. When the conductive layer is electrophoretically deposited at 1 volt, the current changes. As can be seen from the figure, when the electrophoretic deposition time reached about 150 seconds, the current did not change significantly. Therefore, the electrophoretic deposition time used in the present invention ranges from 5 seconds to 200 seconds. The zirconia electrolyte was electrophoretically deposited at a voltage of 1 volt, and the deposition time was 36 seconds, 72 seconds, 108 seconds, 144 seconds, and 180 seconds, respectively. After co-sintering at 1350 ° C, the thickness was 3.08 μm and 5.29 μm, respectively. 6.18 microns, 7.239 microns, 11.38 microns.
參閱第九圖所示，對於以電壓1伏特進行電泳沉積氧化鋯電解質，沉積時間分別為36秒、72秒、108秒、144秒、180秒，再以1350℃進行共燒結後之具氧化鋯電解質的氧化鎳/氧化鋯進行漏氣量測，以PMI孔隙儀量測通孔直徑，持續增加壓力至60psi，其中0.5微米是測孔儀在60psi氣壓下，接近最小量測通孔徑，而沉積72秒所量測通孔徑為0.49μm，後曲線趨勢持平，顯示沉積72秒後，具氧化鋯電解質的氧化鎳/氧化鋯就可承受60psi的壓力而不透氣，一般而言，SOFC的氣壓差不超過14.5psi，60psi遠大於14.5psi，足敷實際需求。 Referring to the ninth figure, for the electrophoretic deposition of zirconia electrolyte at a voltage of 1 volt, the deposition time is 36 seconds, 72 seconds, 108 seconds, 144 seconds, 180 seconds, and then co-sintered at 1350 ° C with zirconia. The electrolyte's nickel oxide/zirconia is measured for leaks. The PMI is used to measure the through-hole diameter and continuously increase the pressure to 60 psi, where 0.5 μm is the pore meter at 60 psi, close to the minimum through-the-hole, and deposited. The measured aperture is 0.49μm in 72 seconds, and the post-curve trend is flat. It shows that after 72 seconds of deposition, the nickel oxide/zirconia with zirconia electrolyte can withstand 60psi pressure and is not gas permeable. Generally, the SOFC pressure difference Not more than 14.5 psi, 60 psi is much greater than 14.5 psi, enough to meet actual demand.
參閱第十圖所示，當該氧化鎳/氧化鋯陽極基材與該氧化鋯電解質進行共燒結時，該導電層可作為氧化鎳/氧化鋯和氧化鋯乾燥收縮和燒結收縮的應力緩衝層，可避免兩者間的界面產生裂痕。 Referring to FIG. 10, when the nickel oxide/zirconia anode substrate is co-sintered with the zirconia electrolyte, the conductive layer can serve as a stress buffer layer for dry shrinkage and sintering shrinkage of nickel oxide/zirconia and zirconia. It can avoid cracks in the interface between the two.
根據上述實驗，本發明可製成薄而緻密的氧化鋯電解質，藉以使SOFC的操作溫度降低，且縮短SOFC工作時氧離子擴散距離。綜合上述實施例之說明，當可充分瞭解本發明之操作、使用及本發明產生之功效，惟以上所述 實施例僅係為本發明之較佳實施例，當不能以此限定本發明實施之範圍，即依本發明申請專利範圍及發明說明內容所作簡單的等效變化與修飾，皆屬本發明涵蓋之範圍內。 According to the above experiment, the present invention can be made into a thin and dense zirconia electrolyte, thereby lowering the operating temperature of the SOFC and shortening the diffusion distance of oxygen ions during operation of the SOFC. In view of the above description of the embodiments, the operation, use and effects of the present invention can be fully understood, but the above The embodiments are merely preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, and the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are covered by the present invention. Within the scope.
(1)‧‧‧氧化鎳/氧化鋯陽極基材 (1)‧‧‧ Nickel Oxide/Zirconium Oxide Anode Substrate
(11)‧‧‧導電層 (11) ‧‧‧ Conductive layer
(2)‧‧‧氧化鋯電解質 (2) ‧ ‧ zirconia electrolyte
(3)‧‧‧金屬鎳陽極基材 (3)‧‧‧Metal nickel anode substrate
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| 張詠策, "電泳沉積法製備固態氧化物燃料電池", 國立交通大學, 材料科學與工程學系, 碩士論文, 2010年(國家圖書館上架日：2011/02/24) Chunwen Sun et al., "Recent anode advances in solid oxide fuel cells", Journal of Power Sources, Vol. 171, June 26 2007, pp.247-260 Zhenjun Jiao et al., "Comparison of ultra-fast microwave sintering and conventional thermal sintering in manufacturing of anode support solid oxide fuel cell", Journal of Power Sources, Vol. 195, June 30 2010, pp.8019-8027 * |
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