TWI620369B - 用於交叉指型共擠製之結構 - Google Patents

用於交叉指型共擠製之結構 Download PDF

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TWI620369B
TWI620369B TW102148349A TW102148349A TWI620369B TW I620369 B TWI620369 B TW I620369B TW 102148349 A TW102148349 A TW 102148349A TW 102148349 A TW102148349 A TW 102148349A TW I620369 B TWI620369 B TW I620369B
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可瑞 柯伯
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Abstract

一種電極結構，包括：一交叉指型層，其具有至少一第一材料及一第二材料，該第二材料具有高於該第一材料或與之類似的電導性，且比該第一材料更具離子電導性，該兩材料之一橫剖面係為非矩形狀。

Description

用於交叉指型共擠製之結構
本發明係有關於一種電極結構。
眾多應用存在於電池、燃料電池、電互連、超級電容及其他來自具有非相似材料之緊密隔開的交叉指型帶的優點之中。這些材料可使用如美國專利公報第2012/0156364號所揭示之共擠製印刷頭，以美國專利第7,799,371號所示之類似但為替代的印刷頭共擠製。在此上下文中，共擠製意指材料在流動時並未混合。不過，所得的結構在橫剖面形式中具有矩形幾何，且沿著垂直交叉指型幾何的方向具有直線均勻的印刷。
然而，模型化已顯示非矩形橫剖面幾何在容量及能量密度中具有性能增強增益。典型地，由狹槽塗布製程或薄膜及半導體製造技術產生電極。對結構化電極的大規模生產而言，這些方法尚未達成成本效益。
10‧‧‧電極結構
12‧‧‧第一材料
14‧‧‧第二材料
16‧‧‧電極結構
18‧‧‧緻密堆積區域
20‧‧‧多孔區域
22‧‧‧電極結構
24‧‧‧緻密堆積區域
26‧‧‧多孔區域
32‧‧‧緻密區域
34‧‧‧區域
36‧‧‧結構
38‧‧‧非矩形區域
40‧‧‧非矩形間隔
42‧‧‧結構
44‧‧‧非矩形區域
46‧‧‧非矩形間隔
50‧‧‧結構
52‧‧‧電流收集器邊界
54‧‧‧陽極
56‧‧‧隔板
58‧‧‧陰極結構
62‧‧‧材料
64‧‧‧材料
第1圖顯示先前技術的交叉指型結構。
第2至3圖顯示交叉指型結構的實施例。
第4圖顯示交叉指型結構的先前技術實施例。
第5至6圖顯示交叉指型結構的實施例。
第7圖顯示電池結構的實施例。
第8及9圖顯示針對先前技術及鋰結構之當前實施例的材料利用圖。
第10圖顯示先前技術及鋰結構之當前實施例之間的放電性能圖。
第11及12圖顯示擠出材料之波狀圖案的實施例。
第1至6圖顯示使用例如美國專利第7,799,371號所示之共擠製印刷頭形成之結構的各種實施例。第1圖顯示電極結構10的先前技術實施例。該結構具有與第二材料14交錯對插之為較寬部分的第一材料12。材料12由緻密堆積的活性電極材料構成，而材料14由高度多孔材料構成，以用於增強的離子電導性或電導性。材料14可具有高出第一材料或與之相同的電導性，且將更可能具有較高的離子電導性。
除了已移除由犧牲材料產生的區域34之外，第4圖顯示類似的先前技術方案。僅餘留例如32之緻密區域。此將允許電解質在電池電極的實施例中銼平該區域。
第2至3圖顯示緻密堆積區域18和24以及多孔區域20和26，該等具有非矩形的橫剖面。通過控 制製程條件(例如，壓力調諧、流體流量率及流體流變性)，可得出結構16及22。關於流體流變性，兩材料的黏度必須與類似的密度匹配。不過，密度可由於導電材料的濃度而改變，但黏度的匹配仍然重要。
區域18及24的非矩形橫剖面允許更佳地控制跨電極結構16及22的濃度梯度。這些結構具有更多暴露至多孔區域之緻密堆積區域的表面面積。跨電池電極之較大的濃度梯度導致較大的歐姆壓降，其影響電池組電池的能量密度及電力密度。藉由控制濃度梯度，可避免大梯度並增加電池組電池的效能。非矩形橫剖面可具有尖銳角或圓角。
第5及6圖顯示類似的結構36及42，其具有緻密堆積材料之非矩形區域38及44以及例如40及46之非矩形間隔。在這些結構中，間隔將填以電解質材料，對電解質暴露出緻密堆積材料的更多表面面積。
第7圖顯示電池模型的簡化方塊圖，其係用於判定非矩形電極橫剖面與矩形橫剖面實施例相比之性能改善。結構50具有電流收集器邊界52。在此實施例中，陽極54由具有位於50微米之範圍內之厚度的鋰箔構成。隔板56分開陽極52與陰極結構58。在此實施例中，陰極結構58由緻密堆積與高度多孔材料的交替區域構成。雖然第7圖的方塊圖將這些區域顯示為矩形，該等實際上具有第2及3圖的形狀。在此實施例中，緻密堆積區域由70%濃度之活性材料的鋰鈷氧化物(LCO)構成，且高度多孔區域由40%濃度的LCO構成。
材料可為任何類型的電池材料，並具有任何範圍的活性材料濃度，但典型地，高度多孔區域將具有較緻密區域少的活性材料。另外，材料可用於除了電池的其他結構中。可使用的材料範例包括鋰鈷氧化物(LCO)、鋰鎳鈷錳氧化物(NCM)或兩者的混合物。其他材料可包括鋰鎳鈷鋁氧化物(NCA)、鋰錳氧化物(LMO)、磷酸鋰鐵(LFeP)。陽極材料可為鈦酸鋰(LTA)。
第8及9圖分別顯示在「1C」放電之後針對第1圖及第2圖之電極結構的材料利用圖，其中所施加的電流密度為12.9mA/cm2。「C」率放電為電池相對於其最大容量之放電率的測量值。「1C」率為電池將在1小時內放電其整個容量的電流。在結構的多孔及緻密區域之間使質量及容積守恆，僅有的差別係橫剖面的幾何。第2圖的結構在1C率下具有勝過第1圖結構之接近10%較大的活性材料利用。
下表中的容量、能量及電力數值顯示各結構之間的相對性能改善，而非可針對鋰鈷氧化物實現之絕對性能改善。第10圖連同下表顯示使用非矩形結構達成之能量、電力及容量增益。在第10圖的圖表上，上部線為第2圖的結構，而下部線為第1圖的結構。該圖顯示，相較於第1圖的結構，第2圖的結構具有較長的運行時間及較低的電壓降。這是因為活性材料利用的增加以及陰極結構中之較低的濃度梯度。
如先前所提及，這些增益並非來自結構中的較高容積或較大質量，僅來自幾何變化。
迄今，討論已聚焦於相對電池電極結構之橫剖面的幾何變化。不過，如先前所提及，控制製程參數可將藉由印刷頭形成的非矩形結構實現為蝕刻遮罩及互連。在此環境中，第5及6圖所示的結構將組成犧牲材料一經移除後遺留的材料。材料可為導電或聚合物，取決於材料在所得結構中的用途。舉例來說，對電路互連而言，材料將是導電的，不是金屬就是導電聚合物，在移除犧牲材料後用作接點。
美國專利公報第2012/0156364號中所討論的印刷頭具有稱之為「掃掠」的流動路徑，其中流動路徑的邊緣及角落係成角及/或成斜角，以減緩可積聚材料的死點。此積聚材料可達到臨界質量，且之後爆裂進入流動路徑，或其可導致流動路徑變成受到壓縮的。在任一情況下，藉由掃掠流動路徑，在表面上所得之材料沈積的均勻性係以直線單片圖案保存之。不過，藉由使用「非掃掠」流動路徑或者藉由使用差壓或機械動作使材料脈動流入印刷頭，可形成至表面上之材料的更為隨機化、波浪形或「波狀」流動圖案。
第11圖顯示這一類隨機化材料圖案之一範例。所得的沈積由兩個不同材料62及64的波狀線構成。如先前所提及，可移除作為犧牲材料的材料之一。移除所留下的空隙可填以不同的材料。或者，餘留的材料可形成互連及接觸墊，或可形成用於下方材料的蝕刻遮罩。
第12圖顯示材料圖案的簡化版本。流動方向係定義為材料從印刷頭開始流動的方向。印刷頭將從最接近觀看者的圖案邊緣開始行進，並拉回遠離觀看者。垂直薄膜的方向將是薄膜的頂視圖。堆疊方向指的是藉由沿著多個平行路徑運行印刷頭來側向堆疊此圖案，以藉由將較小圖案沿著所示方向側向堆疊在一起而形成更大圖案的能力。
以此方式，可藉由形成具有非矩形橫剖面的電極結構來形成更有效率、更高性能之用於電池的電極結構。非矩形結構可通過控制製程參數由具有掃掠流動路徑之預先存在的印刷頭形成，或可由類似預先存在的印刷頭，但具有「非掃掠」路徑的印刷頭形成。類似地，可用作互連的隨機化結構或隨機化蝕刻遮罩可通過製程控制使用預先存在的印刷頭或使用具有非掃掠流動路徑的印刷頭形成。

Claims (6)

  1. 一種電極結構，包括：一交叉指型層，其具有至少第一材料及第二材料，該第二材料：具有比該第一材料的電導性為高或相同的電導性；比該第一材料更具離子電導性；比該第一材料具有更高的多孔性；及比該第一材料具有較少的活性材料；其中該兩材料之橫剖面為梯形，該電極結構係陰極或陽極的任一者，該陰極或陽極與一分離器相鄰設置，使得交替部分沿一堆疊方向成交替，其中該堆疊方向係與該陰極或陽極的任一者相平行，使得與該陰極或陽極相接觸的多孔性是在一較高及較低的多孔性之間交替。
  2. 如請求項1之結構，其中該梯形橫剖面具有尖角。
  3. 如請求項1之結構，其中該梯形橫剖面具有圓角。
  4. 如請求項1之結構，其中該第二材料為一犧牲材料。
  5. 如請求項1之結構，其中該交叉指型層包括一波狀或波浪形圖案之一。
  6. 如請求項1之結構，其中該交叉指型層包括沿著一印刷方向之一直線單片圖案。
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