TWI617065B - 以共擠壓印刷製造的先進且高電力及能量之電池電極 - Google Patents

以共擠壓印刷製造的先進且高電力及能量之電池電極 Download PDF

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TWI617065B
TWI617065B TW102148345A TW102148345A TWI617065B TW I617065 B TWI617065 B TW I617065B TW 102148345 A TW102148345 A TW 102148345A TW 102148345 A TW102148345 A TW 102148345A TW I617065 B TWI617065 B TW I617065B
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昌中 裴
艾利克Ｊ 史雷達
可瑞 柯伯
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帕洛阿爾托研究中心公司
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Abstract

本發明揭示的電池具有陽極、與該陽極相鄰的分隔板，以及與該分隔板相鄰且與該陽極對立的陰極，該陰極包括指叉型(interdigitated)材料條，該材料之一形成孔洞通道。

Description

以共擠壓印刷製造的先進且高電力及能量之電池電極
電池電極設計通常必須在能量密度與電力密度之間權衡。通常能量密度被認為是儲存在給定系統或每單位質量的空間區域中所儲存的能量含量。電力密度是材料傳導電流的能力之量測。典型地，具有高能量密度(亦即高儲存容量)的裝置不會快速放電，意指他們不會同時具有高電力。
對於在電力供應應用中之增加的體積能量密度鋰離子(Li離子)電池有強烈需求。所述需求發生在一些地方，例如長範圍可驅動電動車(EV)、混合動力EV以及無電線的電力工具。特別是關於EV，Li離子供電EV可使用的距離與體積能量密度直接相關。目前鋰離子電池符合或超過美國先進電池協會(USABC)對於電力要求的目標，但是僅符合他們對於體積能量密度建議目標的60%。為了增加Li離子電池的體積密度，重要的是減少Li離子電池中非活性成分的體積。
第1圖顯示典型的Li離子電池10，其中活性材料是由陰極18的鋰-鈷-氧化物(LiCoO2)以及陽極部 分的石墨20組成。非活性成分是由電解質、黏著劑、碳、分隔板14以及正與負電流收集器12與16組成。第2圖顯示在放電過程中，如何透過第1圖中的液體電解質的部分20從陽極至陰極電極發生Li離子傳輸。液體電解質24中離子的局部耗損可發生於電性傳導且緻密的電極。當電流更增加時，此現象限制在放電容量下降的情況下可能產生的臨界電流密度。在習知的Li離子電池中已經使用具有較短Li離子擴散長度22的較薄電極(約100微米)，用以降低此效應。
關於目前的EV應用，藉由堆疊許多層的習知薄電極而產生大電池。這造成這些電池中具有很大部分的非活性成分。減少昂貴分隔板與沉重電流收集器的數量可大幅降低費用與非活性材料存在量。第4圖顯示使用較厚電極(例如36)之Li離子傳輸路徑38提供直接的實用的解決方案，以增加活性材料對非活性材料的比例的方式而增加Li離子電池的體積能量密度。然而，第4圖顯示關於較厚電極(例如36)的問題。由於較長的擴散路徑(例如38)，因此電解質耗損因在擴散路徑中複雜微結構中的不良Li離子傳導性而增加。目前生產製程限制對於電極結構可做的改善。
10‧‧‧鋰離子電池
12‧‧‧正電流收集器
14‧‧‧分隔板
16‧‧‧負電流收集器
18‧‧‧陰極
20‧‧‧石墨、液體電解質的部分
22‧‧‧擴散長度
24‧‧‧電解質
36‧‧‧較厚電極
38‧‧‧路徑
50‧‧‧電池
52‧‧‧電流收集器
54‧‧‧分隔板
56‧‧‧電流收集器
58‧‧‧陰極
60‧‧‧陽極
62‧‧‧基質
64‧‧‧孔洞通道
70‧‧‧指叉型結構之部分
80‧‧‧擴散路徑
82‧‧‧擴散路徑
第1圖與第2圖顯示習知鋰離子的習知技藝配置方式。
第3圖與第4圖顯示使用厚電極增加鋰離子電池的體積能量密度的習知技藝配置方式。
第5圖顯示具有厚的、高能量密度的電極與直孔洞通道的電池之實施例。
第6圖更詳細顯示具有提供快速鋰離子路徑之直孔洞通道的電極之實施例。
第7圖與第8圖顯示在充電與放電過程中，具有直孔洞通道的電極之擴散路徑。
第9圖顯示製造電池電極的方法之實施力的流程圖。
第5圖顯示具有不同形式電極的電池之實施例。電池50具有電流收集器52與56、陰極58、鄰接該陰極的分隔板54，以及與該陽極相鄰且與該陰極對立之陽極60。在此實施例中，該陰極54由指叉型(interdigitated)材料條組成。
這些形式的電池電極範例討論於美國專利7,765,949；7,780,812；7,992,471以及美國專利公開案20120156364以及20120153211。美國專利7,765,949揭示用於將材料擠壓與分配在基板上的裝置，該裝置具有用於接收材料的至少兩個通道以及用於擠壓該材料至該基板上的出口埠。美國專利7,780,812揭示具有平面化邊緣表面的另一裝置。美國專利7,922,471揭示用於擠壓材料的裝置，其具有平衡形狀而不會在沉積於基板上之後平穩下來。美國專利公開案20120156364以及 20120153211揭示共擠壓頭，其將兩種或多種材料流結合至基板上的指叉式結構，該處有多個材料條。
第5圖中的電池50具有陰極，該陰極具有指叉式材料條。這些條可由該共擠壓裝置形成，該共擠壓裝置亦可指上述專利與專利公開案所揭示的印刷頭。此結構可由其他形式的裝置形成。此外，可使用本發明揭示的實施例形成其他形式的結構。電池電極係構成所揭示的材料與實施例之用途的僅一個範例。
習知擠壓方法無法藉由進料多種黏性、顆粒填充漿狀物至印刷頭而使不同液體流交互覆蓋而形成傳導接觸與間隔的指叉型條。由於上述微共擠壓印刷頭中的層流，兩種材料通常不會混合。第6圖顯示第5圖的指叉型結構之部分70的分解圖。
指叉型材料條的材料之一形成孔洞通道，其作為該電極結構內的微結構。該些條的形成及造成此結構所使用的材料將更詳細說明如下。該孔洞通道(例如64)主要作用是成為促使Li離子移動的槽或來源。當該Li離子從另一材料62通過該孔洞通道轉移時，這些通道造成較短且較不曲折的路徑。這使得使用較厚電極是可能的。所得到的陰極具有高電力與體積能量密度。
第7圖與第8圖顯示槽與來源處的擴散路徑。第7圖顯示在充電過程中，通過基質62至該孔洞通道64的擴散路徑80。第8圖顯示在放電過程中，從該孔洞通道至該基質62的擴散路徑82。至該基質的路徑與來自該基質的路徑較短，其中該基質為陰極中另一材 料條，以及該孔洞通道允許非常快速的擴散路徑。
直至此處的討論已經解決結構問題，接下來是關於製造這些結構的方法。第9圖顯示製造指叉式電極的實施例之整體流程圖。通常，該製程涉及混合第一活性材料與溶劑以產生第一電極活性材料，此示於90。該溶劑使得材料變薄，使其更容易流經該共擠壓裝置。該第一活性材料與該第二活性材料通常可為相同材料，但為不同濃度。為了討論目的，該第一材料為具有較高濃度的材料。
用相同方式製備該第二材料，此示於92。而後，使用上述或其他形式的共擠壓裝置或印刷頭，將該兩種活性材料一起被擠壓，此示於94。一旦該材料位於該基板上，移除該溶劑，留下該活性材料在該基板上的各別位置中。而後，藉由提供分隔板(示於98)以及陽極(示於100)而完成該電池。
該製程的目標之一是提供有空隙間隔的分散顆粒尺寸，用於在具有較低活性材料濃度的材料條中形成該孔洞通道。此製程可發生於數種不同方式。此討論針對室溫方法與高溫製程。關於室溫實施例，該活性陰極材料可由鋰鈷氧化物(LCO)、鋰鎳鈷錳氧化物(NCM)或二者的混合物所組成。其他材料可包含鋰鎳鈷鋁氧化物(NCA)、鋰錳氧化物(LMO)、磷酸鋰鐵(LFeP)。雖然本發明的許多活性材料為鋰，但是這些技術可被應用於鈉離子電池與鎂離子電池。該陽極材料可為石墨與鈦酸鋰(LTA)。在此特定實施例中，該材料與黏著劑混合，該黏 著劑例如聚氟化亞乙烯(PVDF)，以及該溶劑是由N-甲基吡咯啶酮(NMP)組成。亦可加入聚氧乙烯油基醚形式的分散劑，亦已知為Brij 98。可加入碳黑增加電傳導性。
這些材料形成兩個不同泥漿，其中一泥漿具有比另一個較高濃度的活性材料。該共擠出裝置將該泥漿沉積在基板上，而後移除該溶劑。在室溫實施例中，自泥漿的乾燥除去該溶劑，留下該材料於個別位置中。
在高溫實施例中，該活性材料由LCO組成。在此實施例中使用的黏著劑是乙基纖維素樹脂，例如陶氏化學公司(Dow Chemical Company)製造的EthocelTM。在此特定實施例中使用的溶劑是由癸二酸二乙酯與丁基卡必醇(butyl cartibol)的混合物組成。該分散劑可由亞麻酸組成。該混合物被沉積，而後在高溫燒結以移除溶劑並且留下該材料。
在任一情況下，所得到的材料具有在低較低濃度中分布廣的顆粒尺寸。這使得形成該孔洞通道，作為該電極中的微結構。所得到的電極具有高受控的微結構，提供快速鋰離子擴散路徑，解決電解質耗損問題，因而製造高能量與電力的電極。相較於習知的電池電極，這些電極顯示更佳的電化學效能。
相對地，習知的電池電極由於典型係由電流收集器箔上的糊狀物製造而成(其中使用薄帶成形(tape casting)塗敷該糊狀物)，因此僅具有簡單的整體微結構。

Claims (5)

  1. 一種電池，包括：陽極；與該陽極相鄰的分隔板；以及與該分隔板相鄰且與該陽極對立的陰極，該陰極包括指叉型(interdigitated)材料條，該材料之一形成孔洞通道；其中該指叉型材料條包括第一材料及第二材料，且該第一材料的鋰濃度低於該第二材料。
  2. 如請求項1之電池，更包括與該陽極及該陰極相鄰且與該分隔板對立的電流收集器。
  3. 如請求項1之電池，其中該陰極包括鋰鈷氧化物或鋰鎳鈷錳氧化物的活性材料。
  4. 如請求項1之電池，其中該陰極包括活性材料，其係以下之一者：鋰鎳鈷鋁氧化物(NCA)、鋰錳氧化物(LMO)或磷酸鋰鐵(LFeP)。
  5. 如請求項1之電池，其中該陽極包括指叉型材料條，所述材料之一形成孔洞通道。
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