200924267 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一項用於固態氧化物燃料電池（S〇Fc)電極 層之製造技術，特別是有關於一種結合造孔劑與燒結技術之創新碉 控程序，以研製出具特定孔隙率與氣體透過率之固態氧化物燃料^ 池之電極層。此製造/生產程序具高可靠度與彈性調整之特性。 【先前技術】 P遺著油價高漲無健識抬頭，再生能_高能源轉化率技術 已成為本世紀最重要的發展技術之一。固態氧化物燃料電池為且備 咼效率、低污染和多元化能源之發電系統，且材料组成簡單、姓 t化與可持續穩定發電之特色，是最具有發展潛力的發電系 其中，平板型固態氧化物燃料電池可克服長電路損失，且電流收集 ，勻i因此可提高電池的功率密度，故平板型_氧化物燃料電& 為現今國際各研究團隊研製與開發之主要對象。 第一代固態氧化物燃料電池之發展是以電解 撐基板（Electrolyte Supported Cell:簡稱ESC)，作由於電解質 J (^120^150«) 溫（約85G〜1_：)操作才能錄佳的電池效能，也使 ，以電極作為支撐基板，其中又以陽極支撐基板單元 滅200924267 IX. Description of the Invention: [Technical Field] The present invention relates to a manufacturing technique for a solid oxide fuel cell (S〇Fc) electrode layer, in particular to a combination of pore former and sintering technology An innovative control program to develop an electrode layer of a solid oxide fuel cell with a specific porosity and gas permeability. This manufacturing/production process is characterized by high reliability and flexibility. [Prior Art] P has a high oil price and no knowledge, and renewable energy _ high energy conversion rate technology has become one of the most important development technologies of this century. Solid oxide fuel cell is a power generation system with high efficiency, low pollution and diversified energy, and has the characteristics of simple material composition, surnamed and sustainable and stable power generation. It is the most promising power generation system, flat solid state. The oxide fuel cell can overcome the long circuit loss, and the current collection and uniformity can increase the power density of the battery. Therefore, the flat type _ oxide fuel electric & is the main object of research and development of various international research teams. The development of the first generation of solid oxide fuel cells is based on Electrolyte Supported Cell (ESC), which is capable of recording battery performance due to electrolyte J (^120^150«) temperature (about 85G~1_:). , also, using the electrode as a supporting substrate, wherein the anode supporting substrate unit is extinguished
Supported Cdl:_ASC)為主要補之電池 以厚度約600微米以上之陽極作為支撐基板，提U = 大提升燃㈣池讀秘顧。目敎界·?= 200924267 力於固態氧化物燃料電池之研發，而 極支撐基板型單元電池’使得固態氧化“也二=夏生產陽 商業化之應用。 物1、科電池之發展即將邁向 固態氧化_料電池之電極層為—多 料氣體與氧化劑氣體之傳輸，而供燃 基板孔隙率之體積百姐齡於1G ，支擇 致電極支#基板之機械強度下降，單的孔隙率會導 率會導致濃度極化，使騎電池^g“糾壞’但低的孔隙 庠ίί!月係提出一種結合造孔劑與燒結技術之創新，程 4寺性’以解決上述 【發明内容】 態氧氣财過率之固Supported Cdl: _ASC) is the main supplement battery. The anode with a thickness of about 600 microns or more is used as the supporting substrate, and U = large boosting (4) pool reading secret.目敎界·?= 200924267 The development of solid oxide fuel cells, and the extremely support substrate type unit battery 'making solid state oxidation' is also the application of commercialization of summer production. The electrode layer of the solid state oxidation battery is the transmission of the multi-material gas and the oxidant gas, and the volume of the porosity of the combustion-supporting substrate is 1G, the mechanical strength of the substrate is decreased, and the porosity of the substrate is reduced. The conductivity will cause the concentration polarization, so that the riding battery will be "corrected" but the low porosity 庠ίί! The moon system proposes an innovation combining the pore-forming agent and sintering technology, to solve the above [invention] Solid state of oxygen
a^IV :，並以球= ϋ構。陽極生胚基板需經高溫燒結程序， 線(c。咖1— 比可佳實施例’上述造侧之成分紅墨，轉量百分 比可為aHG%，或造_數（pQrcF崎細）^=百:匕 匕=迮刮刀成型技術製造:二 200924267 處造孔q指數定義為每卿克陽極粉體所添加造孔劑之重量克數。 、依妝本發明之較佳實施例，上述之燒結溫度可為IB— 1彻。c， Γ溫可為0_2—1。。，降溫速率可為〇·5 -1 r，燒結之氣氛為空 氣’，、氣體流率可為〇 —6〇c.c./min。 【實施方式】 本發明之固態氧化物燃料電池電極層之製造技術，係結合造孔 燒結技術之創新調控程序，以研製出具特定孔隙率與氣體透過 二之，態氧化物燃料電池電極層之製造程序。此技術為研製高發電 功率密度（powerdensity)與高可靠度（reliability) s〇fc_MEA2 生產程序’本項發明至少包括下列步驟： v驟·製作％極支樓基板。首先以重量百分比50¾ NiO、50% 8YSZ (8mol.% Yttria-Stablized Zirconia)與特定量之造 孔劑（石墨，graphite)組成基本材料，添加適當比例之 洛劑（酒精/丁酮(Ethanol/Ethyl Methyl Ketone (MEK)))、 分散劑（三乙醇氨(11^1;1^11〇匕111丨1^(丁£八))）、塑化劑（聚 乙二醇/鄰苯二甲酸二丁酯（p〇lyethylene Glycx)l(；PEGyDibutylphthalate(DBP)))和黏結劑（聚乙烯 縮丁盤(Polyvinyl BUtyral(PVB)))。經由球磨方式均勻混 合後，以刮刀成型技術製造電極生胚，再經層合技術， 製造出厚度約ΙΟΟΟμπι，大小為5x5cm2與l〇xi〇cm2之陽 極生胚（Anode Green Substrate )。 步驟二：將生胚基板經由高溫燒結後可得陽極陶瓷基板（An〇de Ceramic Substrate)或稱陽極支撐基板（如〇扣Supp〇rted Substrate)。生胚基板燒結分為兩循環，第一循環升溫至 1250C，第二循環升溫至1400°C。本發明程序之燒結曲 線有兩種，第一種為升、降溫速率固定在H/min (燒結 曲線A，如第1圖所示），另一種為升溫速率為ο〕— 1。〇, 200924267 降溫速率為Q.5 — 1 °C (燒結曲線B，如第2 ®所示）。择 結之氣氛為空氣，其氣體流率為〇_6〇c c/min。 & 步驟二.利用孔隙度分析儀（PyC_eter)與氣體透過率 Pe^eability)分析儀執行陽極支撐基板之孔隙度（p〇r 與氣财過率量測及鑑定特性。另輔助量測陽極基板之機 強度’供產品品管參閱。 經由上述程序，可製作出特定孔隙率與氣體透過率之固態氧化 燃料電池之電極陶絲板。以下詳細闡述本發明之實施範例： 實施例一 步驟一 H量5〇% Νί〇、 _與特定量之造孔劑（石 土），，且成基本材料，陽極粉料（Ni〇 + 8YSZ之 八 ’造孔劑與陽極粉料之重量百分比為〇—4%刀， 數為〇-4。添加適當比例之 /谷劑（酒精/ 丁鲷）、分散劑（三乙醇氨）、塑化劑（聚乙二 二丁酯）和黏結劑（聚乙烯縮丁朴其重ί 百，分別為 Ϊ5-25%]—2%、2 —3%和3_6% 里 經由球磨方式均勻混人24 4R ,太 设 陽極生胚。再經以到刀成型技術製造 .^ ς c 2 fc，.層σ技術，製造厚度為800 — 1200 μπι，大 小為5x5cm與l〇xl0cm2之生胚基板。 步驟二基板，高溫燒結至歸C，其升、降溫速率固定 第二階段高溫燒結至14〇叱，以增加 序後，鴨經由上述之製造程 200924267 (Poreformerlndex)。由第3圖得知，隨著造孔劑 即增加造孔劑之重量百分比，觸極支撐基板t ’ 會增加，但之後漸鮮緩。這表示造孔_添加可提= 極基板所需之孔隙率，而一般最佳的孔隙率範圍為15 —a^IV :, and with the ball = ϋ structure. The anode green substrate needs to be subjected to a high-temperature sintering process, and the line (c. coffee 1 - is better than the preferred embodiment of the above-mentioned composition of the red ink, the percentage of rotation can be aHG%, or the number of _ (pQrcF fine) ^= Hundreds: 匕匕 = 迮 blade forming technology manufacturing: 2 200924267 The pore forming q index is defined as the weight of the pore-forming agent added per gram of anode powder. According to a preferred embodiment of the invention, the above sintering The temperature can be IB-1. c, the temperature can be 0_2-1. The cooling rate can be 〇·5 -1 r, the sintering atmosphere is air', and the gas flow rate can be 〇-6〇cc/ [Embodiment] The manufacturing technology of the electrode layer of the solid oxide fuel cell of the present invention is combined with the innovative control program of the pore sintering technology to develop an electrode layer of a specific oxide fuel cell with a specific porosity and gas permeability. Manufacturing process. This technology is to develop high power density and high reliability. s〇fc_MEA2 production process' The invention includes at least the following steps: v·Make a % pole substrate. First, by weight 503⁄4 NiO, 50% 8YSZ (8mol.% Yttria-Stablized Zirconia) and a specific amount of pore former (graphite) to form the basic material, add appropriate proportion of the agent (Ethanol / Ethyl Methyl Ketone (MEK)), dispersant (triethanolamine (11^1; 1^11〇匕111丨1^(丁£八)))), plasticizer (polyethylene glycol / dibutyl phthalate (p〇lyethylene Glycx) l ( ;PEGyDibutylphthalate (DBP))) and a binder (Polyvinyl BUtyral (PVB)). After uniform mixing by ball milling, the electrode preform is fabricated by doctor blade forming technique, and then laminated to produce thickness. About πμπι, the size of 5x5cm2 and l〇xi〇cm2 of the anode embryo (Anode Green Substrate). Step 2: the raw substrate is sintered through high temperature to obtain an anode ceramic substrate (An〇de Ceramic Substrate) or anode support substrate (For example, Supp〇rted Substrate.) The raw substrate is sintered in two cycles, the first cycle is heated to 1250 C, and the second cycle is heated to 1400 ° C. There are two sintering curves in the process of the present invention, the first one being liter. The cooling rate is fixed at H/min (sintering curve A, such as As shown in FIG. 1), the other is a temperature elevation rate of ο] - 1.〇, the cooling rate is 200 924 267 Q.5 - 1 ° C (sintering curve B, as shown in the second 2 ®). The atmosphere chosen is air with a gas flow rate of 〇_6〇c c/min. & Step 2. Using the porosity analyzer (PyC_eter) and gas permeability Pe^eability) analyzer to perform the porosity of the anode support substrate (p〇r and gas excess rate measurement and identification characteristics. Another auxiliary measurement anode The machine strength of the substrate is referred to the product quality control. Through the above procedure, the electrode ceramic plate of the solid oxide fuel cell with specific porosity and gas permeability can be produced. The following describes the embodiment of the present invention in detail: Step 1 of the first embodiment The amount of H is 5〇% Νί〇, _ with a specific amount of pore-forming agent (stone), and into the basic material, the anode powder (Ni〇+ 8YSZ 八's pore-forming agent and anode powder weight percentage is 〇 - 4% knife, the number is 〇-4. Add appropriate proportion of / gluten (alcohol / Ding), dispersant (triethanolamine), plasticizer (polybutylene dibutyl ester) and binder (polyethylene) It is 5% 5-25%] - 2%, 2 - 3%, and 3_6%. .^ ς c 2 fc,. Layer σ technology, manufactured to a thickness of 800 — 1200 μπι, large The substrate is small 5x5cm and l〇xl0cm2. Step 2: The substrate is sintered at a high temperature to C. The rate of rise and fall is fixed in the second stage and then sintered to 14〇叱 in order to increase the sequence. The duck passes the above manufacturing process 200924267 (Poreformerlndex). It can be seen from Fig. 3 that as the pore-forming agent increases the weight percentage of the pore-forming agent, the tactile support substrate t' will increase, but then gradually become fresher. This means that the pore-forming addition can be increased. The porosity required for the substrate, while the general optimum porosity range is 15 —
%。但過高的造孔劑指數除了對孔隙率的增加幅产右 外，對陽極支撐基板的機械強度與生產良率也會^< 此需特別注意造孔劑的添加量。 9 - ’ U f 實施例. 利用氣體透過率測試儀，針對所得之陽極支撐基板 分析。請參閱第4圖，其顯示在不同造孔劑指數= 支稽基板孔隙率與氣體透過率之關係，橫軸表示孔率 (%) ’縱軸表示氣體透過率（L/cm2/sec)。由第4圖得知, 隨著孔隙率的增加，氣體透過率也大幅提升，因此^ 氣體在陽極基板内外間的傳輸與反應的進行。 步驟一：以重量百分比50%NiO、50% 8YSZ與特定量之造孔劑（石 墨）組成基本材料’陽極粉料（Ni〇 + 8YSZ)之重量百八 比為35- 80%，造孔劑之重量百分比為〇 5 _ 4 %，或造孔& 指數為0.5 -4。添加適當比例之溶劑（酒精/丁酮）、分散劑 (三乙醇氨）、塑化劑（聚乙二醇/鄰苯二曱酸二丁酷）和& 結劑（聚乙烯縮丁醛）’其重量百分比分別為15_25 %、j — 2 %、2 - 3 %和3 - 7 %。之後，經由球磨方式均勻混合24 — 48小時，以刮刀成型技術製造陽極生胚。再經層合技術， 製造厚度800- 1200 μιη ’大小為5x5cm2與10x10 cm2之生 胚基板。 步驟二：。將生胚經由高溫燒結至125〇。〇，其升溫速率為〇.2 _ 1 C/min，降溫速率為rc/min，再進行第二階段高溫燒結 至1400C，以增加陽極基板強度，其升溫速率為ο: _ 1 C/min，降溫速率為rc/min ’（燒結曲線B)。燒結可依 需要通入空乳，其氣體流率為1 - 60 c.c./min。經由上述之製 200924267 造程序後，即可獲得陽極支撐基板。 步驟三：利用孔隙度分析儀與氣體透過率測試儀，針對所得之陽極 支樓基板進行分析，分析結果請參閱第5圖。由第5时 知’燒結時通入適當的空氣流量，陽極支撐基板的孔隙| 大於215 % (體積百分比），氣體透過率也大於lxl〇·4 L/cm/sec，而造孔劑的添加並沒有顯著的提升效果。 第6 _顯示在不同燒結曲線與燒結氣氛下之陽 ΐί ϊίί與氣體透過率之關係（紅色空心圓為燒結曲 線^，藍色工心三角型為燒結曲線Β)。由第6圖得知， 的升溫速率下（燒結麟Β)，陽極支雜板之孔隙率 明顯降低，但可藉由通人空氣的流率來 控術極支撐基板之⑽顿氣體透過率%. However, the excessively high pore-forming index will produce a mechanical strength and production yield to the anode supporting substrate in addition to the increase in porosity. This requires special attention to the amount of pore-forming agent added. 9 - ' U f Example. Analysis of the resulting anode support substrate using a gas permeability tester. Please refer to Fig. 4, which shows the relationship between the porosity of the substrate and the gas permeability of the different pore former index, the horizontal axis represents the porosity (%), and the vertical axis represents the gas permeability (L/cm2/sec). As is apparent from Fig. 4, as the porosity increases, the gas permeability is also greatly increased, so that the gas is transported and reacted inside and outside the anode substrate. Step 1: The weight percentage of 50% NiO, 50% 8YSZ and a specific amount of pore former (graphite) is the basic material 'anode powder (Ni〇 + 8YSZ), the weight ratio is 35-80%, the pore former The weight percentage is 〇5 _ 4%, or the pore making & index is 0.5 -4. Add appropriate proportion of solvent (alcohol / butanone), dispersant (triethanolamine), plasticizer (polyethylene glycol / dibutyl phthalate) and & binder (polyvinyl butyral) 'The weight percentages are 15_25 %, j - 2 %, 2 - 3 % and 3 - 7 %, respectively. Thereafter, the mixture was uniformly mixed by ball milling for 24-48 hours to produce an anode green body by a doctor blade forming technique. Further, a laminate substrate having a thickness of 800 to 1200 μm and a size of 5 x 5 cm 2 and 10 x 10 cm 2 is produced by lamination technique. Step two: The green embryos were sintered to 125 Torr via high temperature. 〇, the heating rate is 〇.2 _ 1 C / min, the cooling rate is rc / min, and then the second stage of high temperature sintering to 1400C to increase the strength of the anode substrate, the heating rate is ο: _ 1 C / min, The cooling rate is rc/min ' (sintering curve B). Sintering can be carried out as needed, and the gas flow rate is 1 - 60 c.c. / min. After the fabrication of the above-mentioned system 200924267, the anode supporting substrate can be obtained. Step 3: Analyze the obtained anode support substrate using a porosity analyzer and a gas permeability tester. For the analysis results, refer to Figure 5. From the 5th time, 'the proper air flow rate is applied during sintering, the pores of the anode supporting substrate| is greater than 215% (volume percentage), the gas permeability is also greater than lxl〇·4 L/cm/sec, and the pore former is added. There is no significant improvement. The sixth _ shows the relationship between the 烧结 ϊ ϊ ίίί and the gas transmission rate under different sintering curves and sintering atmosphere (the red hollow circle is the sintering curve ^, and the blue working core triangle is the sintering curve Β). It can be seen from Fig. 6 that at the heating rate (sintering), the porosity of the anode-doped plate is significantly reduced, but the gas permeability of the electrode-supporting substrate can be controlled by the flow rate of the air.
==旨數(燒結曲線Α)或空氣流曲S 下之祕捕基板氣體透過率之關係 ixi〇-4L/cm 獲得高氣體透過率之陽極支撐基板，但 所有產品之操倾件與分析結果請參 經由實施例之結果發現，燒結曲線Β 有限，右配5&、，，0軋氛與通入氣體流率， (?LP^ ，請 200924267 應視為本發明的進一步實施内函。 因此本發明之保護範圍當以後附之申請專利範圍所界定者為準。 表一 產品編號 造孔劑指數 燒結曲線 氣體體積流率 (c.c./min) 孔隙率 (vol. %) 氣體透過率 (L/cm2/sec) S-17 0 A 0 4.18 2.79x10-6 S-18 2.65 A 0 21.01 2.18x10-4 S-23 1 A 0 14.53 5.10X10·5 S-24 2 A 0 21.16 2.02x10-4 S-28 (60%YSZ) 1 A 0 7.44 2.78xl0'5 S-29 (65%YSZ) 0 A 0 1.09 2.08xl0'6 S-31 3 A 0 25.96 3·04χ10·4 S-32 4 A 0 28.35 7.68xl0-4 S-33 3 B 0 5.05 5.33xl〇·6 S-33A 3 B 58 (air) 19.30 6.02x1 O'4 S-35A 4 B 20 (air) 33.20 4.07xl0'4 S-36A 2 B 12 (air) 30.57 6.02x1 O'4 S-37A 2 B 20 (air) 17.84 9.75XHT5 S-38A 0 B 40 (air) 22.14 1.96xl〇·4 12 200924267 【圖式簡單說明】 f)，生胚基板燒結循環溫控設定A (簡稱燒結曲線 楚一 （a)第一猶環及(b)第二循環。 ίΓΓϋΐ生t基板燒結循溫控設定6 (簡稱燒結曲線 笛- ϋ)第一#環及⑼第二猶環。 弟一圖係為造孔劑之添加量與陽極 ί=;:=同造孔劑指數下之陽“撐基:二 數細流率下之陽極支樓基 繼调極支撐基 第七圖係顯示在(a)不同造丨二& / 空氣流通量（燒結曲線民^ (_燒結曲線A)或（b)不同 陽極支撐基板氣體透過率之θ關係表不PoreF〇而erlndex)下之 【主要元件符號說明】==The number (sintering curve Α) or the relationship between the gas permeability of the substrate under the air flow curve S ixi〇-4L/cm The anode support substrate with high gas permeability is obtained, but the tilting and analysis results of all products Referring to the results of the examples, it is found that the sintering curve Β is limited, and the right 5&,,, 0 rolling atmosphere and the flow rate of the incoming gas, (?LP^, please 200924267 should be regarded as a further implementation letter of the present invention. The scope of protection of the present invention is defined by the scope of the appended claims. Table 1 Product No. Poreing Agent Index Sintering Curve Gas Volume Flow Rate (cc/min) Porosity (vol. %) Gas Transmission Rate (L/ Cm2/sec) S-17 0 A 0 4.18 2.79x10-6 S-18 2.65 A 0 21.01 2.18x10-4 S-23 1 A 0 14.53 5.10X10·5 S-24 2 A 0 21.16 2.02x10-4 S- 28 (60%YSZ) 1 A 0 7.44 2.78xl0'5 S-29 (65%YSZ) 0 A 0 1.09 2.08xl0'6 S-31 3 A 0 25.96 3·04χ10·4 S-32 4 A 0 28.35 7.68 Xl0-4 S-33 3 B 0 5.05 5.33xl〇·6 S-33A 3 B 58 (air) 19.30 6.02x1 O'4 S-35A 4 B 20 (air) 33.20 4.07xl0'4 S-36A 2 B 12 (air) 30.57 6.02x1 O'4 S-37A 2 B 20 (air) 17.84 9.7 5XHT5 S-38A 0 B 40 (air) 22.14 1.96xl〇·4 12 200924267 [Simple description of the diagram] f), the raw material substrate sintering cycle temperature control setting A (referred to as the sintering curve Chu Yi (a) the first Yuhuan and (b) The second cycle. ΓΓϋΐ ΓΓϋΐ t t substrate sintering cycle temperature control setting 6 (referred to as sintering curve flute - ϋ) first #环 and (9) second yue ring. Brother 1 is the amount of pore-forming agent and anode ί =;:=Yang under the pore-forming agent index "support base: the second diagram of the anode support base under the second-order fine flow rate is shown in (a) different ostomy two & / air flow (Sintering curve ^ (Sintering curve A) or (b) θ relationship of gas permeability of different anode supporting substrates is not shown in PoreF〇 and erlndex) [Main component symbol description]