TWI662007B - 用於固態氧化物燃料電池的陰極材料及其製法 - Google Patents

用於固態氧化物燃料電池的陰極材料及其製法 Download PDF

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TWI662007B
TWI662007B TW106141532A TW106141532A TWI662007B TW I662007 B TWI662007 B TW I662007B TW 106141532 A TW106141532 A TW 106141532A TW 106141532 A TW106141532 A TW 106141532A TW I662007 B TWI662007 B TW I662007B
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cathode material
chemical formula
material according
preparing
sodium
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TW106141532A
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TW201925138A (zh
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Sea-Fue Wang
王錫福
Yi-xin LIU
劉怡心
Tung LIN
林彤
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National Taipei University Of Technology
國立臺北科技大學
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Abstract

一種用於固態氧化物燃料電池的陰極材料，包含如下所示的鈣鈦礦型複合氧化物：Gd1-xMxCoO3-δ。其中，M表示一鹼金屬元素；x大於0且不大於0.030；及δ的範圍為0至2。本發明亦提供一種製備如上所述的陰極材料的方法。本發明陰極材料具有較鈣鈦礦型陶瓷氧化物材料GdCoO3更高的導電率。

Description

用於固態氧化物燃料電池的陰極材料及其製法
本發明是有關於一種用於固態氧化物燃料電池的陰極材料，特別是指一種包含經摻雜的鈣鈦礦型(perovskite type)複合氧化物的陰極材料及其製備方法。
鈣鈦礦型(Perovskite type)的陶瓷氧化物(ABO3)具有良好的熱穩定性、機械強度及導電率，因此常用於低汙染且發電效率高的固態氧化物燃料電池(solid oxide fuel cell,SOFC)；其中，含有Co的陶瓷氧化物(ACoO3)由於容易接受電子，因此常用於SOFC的陰極材料。然而，由於固態氧化物的高活化能，使得SOFC的操作溫度往往需高達800~1000℃，可在較低操作溫度(例如500~800℃)中操作並符合導電率需求的鈣鈦礦型陶瓷氧化物材料亟待開發。
Solid State Ionics 86-88(1996)1187-1190揭露一種用於SOFC的鈣鈦礦型複合氧化物Gd1-xSrxCoO3，其具有較鈣鈦礦型陶瓷氧化物材料GdCoO3更高的導電率。
Physics of the Solid State,49(2007)1498-1506揭露GdCoO3、Gd0.9Sr0.1CoO3及Gd0.9Ba0.1CoO3在低溫中的電磁性質。
因此，本發明之目的，即在提供一種用於固態氧化物燃料電池的陰極材料，可以克服上述先前技術的缺點。
於是，本發明用於固態氧化物燃料電池的陰極材料包含一如下化學式1所示的鈣鈦礦型複合氧化物：〔化學式1〕 Gd1-xMxCoO3-δ
在化學式1中，M表示一鹼金屬元素；x大於0且不大於0.030；及δ的範圍為0至2。
因此，本發明之另一目的，即在提供一種製備用於固態氧化物燃料電池的陰極材料的方法，包含以下步驟：(a)處理一第一混合物以得到一如下化學式1所示的鈣鈦礦型複合氧化物：〔化學式1〕 Gd1-xMxCoO3-δ
在化學式1中，M、x及δ的定義如上所述，該第一混合物包括氧化釓(III)、四氧化三鈷及一含有該鹼金屬元素M的先質(precursor)；(b)將該鈣鈦礦型複合氧化物研磨成粉末；(c)混合該粉末及一黏結劑(binder)，以得到一第二混合物；處理該第二混合物以得到一生壓胚(green compact)；及(e)將該生壓胚進行燒結(sinter)以得到該陰極材料。
本發明之功效在於：該用於固態氧化物燃料電池的陰極材料在較低操作溫度中具有較鈣鈦礦型陶瓷氧化物材料GdCoO3更高的導電率。
以下將就本發明內容進行詳細說明：較佳地，在本發明的陰極材料中，在化學式1中，M表示Na，且x的範圍為0.005至0.030。
較佳地，在本發明的陰極材料中，在化學式1中，M表示K，且x的範圍為0.005至0.025。
較佳地，在本發明的製備陰極材料的方法中，該步驟(a)是藉由煆燒(calcination)而進行。
較佳地，在本發明的製備陰極材料的方法中，該含有該鹼金屬元素M的先質是選自於碳酸鈉、硝酸鈉、氫氧化鈉、乙醇鈉、碳酸氫鈉、過氧化鈉、碳酸鉀、硝酸鉀、氫氧化鉀、亞硝酸鉀或氯化鉀。
較佳地，在本發明的製備陰極材料的方法中，該鹼金屬元素M為Na，且該含有Na的先質的鈉元素與氧化釓(III)的釓元素之莫耳比值範圍為5×10-3~31×10-3。
較佳地，在本發明的製備陰極材料的方法中，該鹼金屬元素M為K，且該含有K的先質的鉀元素與氧化釓(III)的釓元素之莫耳比值範圍為5×10-3~26×10-3。
較佳地，在本發明的製備陰極材料的方法中，該步驟(d)是藉由壓製(pressing)成型而進行。
較佳地，在本發明的製備陰極材料的方法中，在該步驟(e)中，該燒結溫度的範圍為1150~1350℃。
較佳地，在本發明的製備陰極材料的方法中，該黏結劑是選自於聚乙烯醇(PVA)、石蠟(paraffin wax)、聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)、聚甲基丙烯酸甲酯(PMMA)、乙烯-醋酸乙烯酯共聚物(EVA)或乙烯-丙烯酸乙酯共聚物(EEA)。
本發明將就以下實施例來作進一步說明，但應瞭解的是，該等實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。
[實施例]
<實施例1>包含Gd 0.990 Na 0.010 CoO 3-δ 的陰極材料E1
將Gd2O3、Na2CO3、Co3O4粉末(純度皆為99.5%以上)以0.990：0.005：0.333的莫耳比例混合，置入裝有3mm之氧化鋯球的PE球磨罐內(混合粉末與氧化鋯球的重量比為1：10)，並加入乙醇進行球磨24小時，出漿後置於烘箱中以90℃乾燥，乾燥後得到一粉體。將得到的粉體置於研缽中並搗碎，接著置於氧化鋁坩鍋中，在高溫爐內以5℃/min的速率升溫至950℃並維持溫度4小時以進行煆燒，得到Gd0.990Na0.010CoO3-δ粉體(即第一混合物)。
將Gd0.990Na0.010CoO3-δ粉體置入裝有氧化鋯球的PE球磨罐內(混合粉末與氧化鋯球的重量比為1：10)，並加入乙醇進行球磨24小時，以降低煆燒造成的團聚現象，出漿後置於烘箱中以90℃乾燥，乾燥後得到一粉末。
在得到的粉末中添加5wt%黏結劑(15wt% PVA水溶液，以該粉末為95wt%)，混合造粒後(即第二混合物)以80mesh 的篩網過篩。接著取0.3g篩下的粉末置入圓形碟狀模具中，藉由單軸冷壓機以成型壓力150Mpa加壓30s，得到一直徑約為9mm、厚度約為2mm的生壓胚。
將該生壓胚置於氧化鋁坩鍋中，在高溫爐內以5℃/min的速率升溫至550℃並維持溫度4小時以去除黏結劑，接著以5℃/min的速率升溫至1250℃(由最佳化實驗得知緻密化程度最高時的溫度)並維持溫度4小時以進行燒結，得到實施例1的陰極材料E1。
<實施例2>包含Gd 0.980 Na 0.020 CoO 3-δ 的陰極材料E2
實施例2的製程與實施例1類似，差異之處在於將上述實施例1中Gd2O3、Na2CO3、Co3O4的莫耳比例改變為0.980：0.010：0.333，得到實施例2的陰極材料E2。
<實施例3>包含Gd 0.975 Na 0.025 CoO 3-δ 的陰極材料E3
實施例3的製程與實施例1類似，差異之處在於將上述實施例1中Gd2O3、Na2CO3、Co3O4的莫耳比例改變為0.975：0.0125：0.333，得到實施例3的陰極材料E3。
<實施例4>包含Gd 0.970 Na 0.030 CoO 3-δ 的陰極材料E4
實施例4的製程與實施例1類似，差異之處在於將上述實施例1中Gd2O3、Na2CO3、Co3O4的莫耳比例改變為0.970：0.015：0.333，得到實施例4的陰極材料E4。
<實施例5>包含Gd 0.950 Na 0.050 CoO 3-δ 的陰極材料E5
實施例5的製程與實施例1類似，差異之處在於將上述實施例1中Gd2O3、Na2CO3、Co3O4的莫耳比例改變為0.950：0.025：0.333，得到實施例5的陰極材料E5。
<實施例6~10>包含Gd 1-x K x CoO 3-δ 的陰極材料E6~E10
實施例6~10的製程分別與實施例1~5類似，差異之處在於將上述實施例1~5中的Na2CO3改變為K2CO3，分別得到實施例6~10的陰極材料E6~E10。
<實施例11>包含Gd 0.925 K 0.075 CoO 3-δ 的陰極材料E11
實施例11的製程與實施例6類似，差異之處在於將上述實施例6中Gd2O3、K2CO3、Co3O4的莫耳比例改變為0.925：0.0375：0.333，得到實施例11的陰極材料E11。
<比較例>包含GdCoO 3 的陰極材料CE
比較例的製程與實施例1類似，差異之處在於將上述實施例1中Gd2O3、Na2CO3、Co3O4的莫耳比例改變為1：0：0.333，得到比較例的陰極材料CE。
[導電率(Electrical conductivity,σ)的測量]
分別將實施例1~11及比較例的陰極材料E1~E11及CE製成長30mm、寬4mm、高2mm的長方體(將上述混合造粒後得到的第二混合物置入長度為30mm的模具中，以成型壓力300Mpa加壓60s，經燒結後裁切而得)，將其六面磨平，分別以銀線連接電化學分析儀，分別在500、600、700、800℃中量測其在固定電流下的電壓值，換算得到電阻值後計算得到導電率(σ)，結果分別如下表1所示。
由表1可以得知，相較於比較例的陰極材料CE，實施例1~11之陰極材料E1~E11的導電率在500℃中具有較GdCoO3更高的導電率；其中，實施例1~4之陰極材料E1~E4及實施例6~11之陰極材料E6~E11在500~700℃中具有較GdCoO3更高的導電率；特別是，實施例6~8之陰極材料E6~E8在500~800℃中具有較GdCoO3更高的導電率。
綜上所述，本發明的陰極材料在較低操作溫度中具有較GdCoO3更高的導電率，故確實能達成本發明之目的。
惟以上所述者，僅為本發明之實施例而已，當不能以此限定本發明實施之範圍，凡是依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。

Claims (10)

  1. 一種用於固態氧化物燃料電池的陰極材料，包含一如下化學式1所示的鈣鈦礦型複合氧化物：〔化學式1〕 Gd1-xMxCoO3-δ在化學式1中，M表示一鹼金屬元素；x大於0且不大於0.030；及δ的範圍為0至2。
  2. 如請求項1所述的陰極材料，其中，在化學式1中，M表示Na，且x的範圍為0.005至0.030。
  3. 如請求項1所述的陰極材料，其中，在化學式1中，M表示K，且x的範圍為0.005至0.025。
  4. 一種製備用於固態氧化物燃料電池的陰極材料的方法，包含以下步驟：(a)處理一第一混合物以得到一如下化學式1所示的鈣鈦礦型複合氧化物：〔化學式1〕 Gd1-xMxCoO3-δ在化學式1中，M、x及δ的定義如請求項1所述，該第一混合物包括氧化釓(III)、四氧化三鈷及一含有該鹼金屬元素M的先質；(b)將該鈣鈦礦型複合氧化物研磨成粉末；(c)混合該粉末及一黏結劑，以得到一第二混合物；(d)處理該第二混合物以得到一生壓胚；及(e)將該生壓胚進行燒結以得到該陰極材料。
  5. 如請求項4所述的製備陰極材料的方法，其中，該步驟(a)是藉由煆燒而進行。
  6. 如請求項4所述的製備陰極材料的方法，其中，該含有該鹼金屬元素M的先質是選自於碳酸鈉、硝酸鈉、氫氧化鈉、乙醇鈉、碳酸氫鈉、過氧化鈉、碳酸鉀、硝酸鉀、氫氧化鉀、亞硝酸鉀或氯化鉀。
  7. 如請求項4所述的製備陰極材料的方法，其中，該鹼金屬元素M為Na，且該含有Na的先質的鈉元素與氧化釓(III)的釓元素之莫耳比值範圍為5×10-3~31×10-3。
  8. 如請求項4所述的製備陰極材料的方法，其中，該鹼金屬元素M為K，且該含有K的先質的鉀元素與氧化釓(III)的釓元素之莫耳比值範圍為5×10-3~26×10-3。
  9. 如請求項4所述的製備陰極材料的方法，其中，該步驟(d)是藉由壓製成型而進行。
  10. 如請求項4所述的製備陰極材料的方法，其中，在該步驟(e)中，該燒結溫度的範圍為1150~1350℃。
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Nunzio Russo, Stefania Furfori, Debora Fino , Guido Saracco, Vito Specchia；" Lanthanum cobaltite catalysts for diesel soot combustion"； Applied Catalysis B: Environmental 83 (2008) 85–95
Nunzio Russo, Stefania Furfori, Debora Fino , Guido Saracco, Vito Specchia；" Lanthanum cobaltite catalysts for diesel soot combustion"； Applied Catalysis B: Environmental 83 (2008) 85–95 陳柏安,許正興；「以固態反應法製備MgTiTa2O8陶瓷與其微波介電特性之探討」；2007年中華民國陶業研究學會會員大會論文 *
陳柏安,許正興；「以固態反應法製備MgTiTa2O8陶瓷與其微波介電特性之探討」；2007年中華民國陶業研究學會會員大會論文。

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