TW202225122A - 鋰金屬氧化物/石榴石複合薄膜及其製造方法 - Google Patents

鋰金屬氧化物/石榴石複合薄膜及其製造方法 Download PDF

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TW202225122A
TW202225122A TW110130867A TW110130867A TW202225122A TW 202225122 A TW202225122 A TW 202225122A TW 110130867 A TW110130867 A TW 110130867A TW 110130867 A TW110130867 A TW 110130867A TW 202225122 A TW202225122 A TW 202225122A
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garnet
lithium
composite ceramic
sintered composite
phase
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邁克愛德華 巴汀
英宏 陳
艾倫大衛 德喬治
真 宋
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美商康寧公司
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Abstract

燒結複合陶瓷，包括：鋰-石榴石主相；以及鋰枝晶生長抑制劑微量相，使得鋰枝晶生長抑制劑微量相，基於燒結複合陶瓷之總重量，具有＞0-10 wt.%之範圍中之Li金屬氧化物。

Description

鋰金屬氧化物/石榴石複合薄膜及其製造方法
本申請案根據專利法主張於2020年08月21日提出申請之美國臨時申請案第63/068,506號之優先權權益，本申請案仰賴該申請案之內容並且該申請案的內容以引用之形式全部倂入本文。
此揭示關於具改進的臨界電流密度(CCD)之鋰-石榴石複合陶瓷電解質。
已廣泛地研究習知的鋰(Li)-離子電池，但仍受限於電容密度、能量密度，及安全性考量，對於電氣設備中之大規模應用造成挑戰。舉例來說，儘管基於Li-石榴石電解質(LLZO)之固態鋰電池解決安全性考量，肇因於剛性陶瓷性質及石榴石之不良鋰可濕性之Li陽極和石榴石電解質間之接觸不足，以及表面雜質，經常導致大的極化及大的界面電阻，從而造成鋰之不均勻沉積以及鋰枝晶形成。
因此，作為Li陽極與石榴石電解質間之不良接觸的結果，電池可能經歷低臨界電流密度(CCD)及最終短路。
本申請案揭露固態鋰金屬電池應用中用於Li-石榴石電解質之增進的晶粒邊界黏合之改進的鋰-石榴石複合陶瓷電解質。
於一些實施例中，燒結複合陶瓷，包含：鋰-石榴石主相；以及鋰枝晶生長抑制劑微量相，其中鋰枝晶生長抑制劑微量相包含，基於燒結複合陶瓷之總重量，＞0-10 wt.%之範圍中之Li-金屬氧化物。
於可與任何其他態樣或實施例組合之一態樣中，鋰-石榴石主相包含下列之至少一者：(i) Li 7-3aLa 3Zr 2L aO 12，其中L=Al、Ga或Fe及0＜a＜0.33；(ii) Li 7La 3-bZr 2M bO 12，其中M=Bi、Ca，或Y及0＜b＜1；(iii) Li 7-cLa 3(Zr 2-c, N c)O 12，其中N=In、Si、Ge、Sn、Sb、Sc、Ti、Hf、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y、Mg、Ca或彼等的組合及0＜c＜1，或彼等的組合。於可與任何其他態樣或實施例組合之一態樣中，鋰-石榴石主相包含：Li 7-cLa 3(Zr 2-c, N c)O 12，其中N=Ta、Ga、W或彼等的組合，及0＜c＜1。於可與任何其他態樣或實施例組合之一態樣中，Li-金屬氧化物包含：Li-矽酸鹽、Li-鎵酸鹽、Li-鋁酸鹽、Li-鎢酸鹽、Li-莫林那特(molinate) 、Li-Ta氧化物、Li-Nb-氧化物、Li-Sn-氧化物、Li-In-氧化物、Li-As-氧化物、Li-Sb-氧化物、Li-磷酸鹽，或彼等的組合。
於可與任何其他態樣或實施例組合之一態樣中，金屬氧化物包含Li-矽酸鹽。於可與任何其他態樣或實施例組合之一態樣中，鋰-石榴石主相包含至少90 wt.%之鋰石榴石立方晶相。於可與任何其他態樣或實施例組合之一態樣中，針對代表至少5%之總晶粒群體之晶粒群體所測量之最大晶粒尺寸不超過總晶粒群體之平均晶粒尺寸的多於20倍。於可與任何其他態樣或實施例組合之一態樣中，燒結複合陶瓷包含具有於30-150 µm之範圍中之厚度的薄膜。於可與任何其他態樣或實施例組合之一態樣中，薄膜具有至少10 -4S/cm之Li-離子導電率以及薄膜之理論最大密度之至少90%的相對密度。
於一些實施例中，電池包含：至少一個鋰電極；以及與至少一個鋰電極接觸之電解質，其中電解質為包含如本文中所描述之燒結複合陶瓷的鋰-石榴石複合電解質。
於一些實施例中，燒結複合陶瓷，包含：鋰-石榴石主相；以及鋰枝晶生長抑制劑微量相，其中：鋰-石榴石主相包含：Li 7-cLa 3(Zr 2-c, N c)O 12，其中N=Ta、Ga、W或彼等的組合，及0＜c＜1，以及鋰枝晶生長抑制劑微量相包含，基於燒結複合陶瓷之總重量，於＞0-10 wt.%之範圍中之Li-矽酸鹽。
於可與任何其他態樣或實施例組合之一態樣中，鋰-石榴石主相包含至少90 wt.%之鋰石榴石立方晶相。於可與任何其他態樣或實施例組合之一態樣中，針對代表至少5%之總晶粒群體之晶粒群體所測量之最大晶粒尺寸不超過總晶粒群體之平均晶粒尺寸的多於20倍。於可與任何其他態樣或實施例組合之一態樣中，燒結複合陶瓷包含具有於30-150 µm之範圍中之厚度的薄膜。
於一些實施例中，燒結複合陶瓷，包含：鋰-石榴石主相；以及鋰枝晶生長抑制劑微量相，其中燒結複合陶瓷包含下列之至少一者：至少10 -4S/cm之Li離子導電率；以及薄膜之理論最大密度之至少90%之相對密度。
於一些實施例中，方法包含以下步驟：於950°C至1500°C之範圍中的溫度燒結金屬氧化物組分/石榴石生胚薄帶以形成複合陶瓷，複合陶瓷包含：鋰-石榴石主相；以及鋰枝晶生長抑制劑微量相，其中鋰枝晶生長抑制劑微量相包含，基於燒結複合陶瓷之總重量，於＞0-10 wt.%之範圍中之Li-金屬氧化物。
於可與任何其他態樣或實施例組合之一態樣中，燒結步驟包含以下步驟：自室溫加熱至溫度範圍；保持於溫度範圍持續1-20分鐘之範圍中之時段；自溫度範圍冷卻至室溫，其中：用於加熱步驟之升溫速率(HRR)為100°C/分鐘＜HRR＜1000°C/分鐘，及用於冷卻步驟之冷卻速率(CR)為100°C/分鐘＜CR＜1000°C/分鐘。於可與任何其他態樣或實施例組合之一態樣中，HRR為250°C/分鐘＜HRR＜750°C/分鐘、CR為250°C/分鐘＜CR＜750°C/分鐘，及溫度範圍為1100°C至1300°C。於可與任何其他態樣或實施例組合之一態樣中，燒結複合陶瓷包含下列之至少一者：至少10 -4S/cm之Li-離子導電率；以及薄膜之理論最大密度之至少90%之相對密度。
於可與任何其他態樣或實施例組合之一態樣中，金屬氧化物組分/石榴石生胚薄帶係藉由以下步驟形成：使過量Li來源與添加劑反應以形成Li-金屬氧化物(LMO)前驅物；使LMO前驅物與鈍化石榴石粉末混合以形成石榴石懸浮物；添加分散劑、黏合劑，及增塑劑至石榴石懸浮物以形成粉漿組成物(slip composition)；以及薄帶鑄造(tape casting)粉漿組成物。於可與任何其他態樣或實施例組合之一態樣中，添加劑包含下列之至少一者：矽氧烷、三氧化鎢(WO 3)，及氧化鎵(Ga 2O 3)。於可與任何其他態樣或實施例組合之一態樣中，金屬氧化物組分/石榴石生胚薄帶係藉由以下步驟形成：混合過量Li來源、Li-金屬氧化物(LMO)前驅物，及鈍化石榴石粉末以形成石榴石懸浮物；添加分散劑、黏合劑，及增塑劑至石榴石懸浮物以形成粉漿組成物；以及薄帶鑄造粉漿組成物。
將仔細參照於附圖中說明之例示性實施例。當可能時，於通篇圖式中將使用相同的元件符號表式相同或類似部件。圖式中的構件不必然依比例，重點反而在說明例示性實施例之原則。應理解的是，本案不受限於描述中提出或圖式中說明的細節或方法。亦應理解的是，術語僅為說明之緣故且不應視為限制。
此外，此說明書中提出之任何實例為說明性的，但非限制性的，且僅於請求之發明之許多可行實施例之一些中提出。對所屬技術領域通常遇到的各種條件和參數進行其他適當的修改和調整，且彼等對發明所屬技術領域中具有通常知識者將為顯而易見的，都落於此揭示之精神及範疇中。 定義
「主相」、「第一相」，或類似術語或措辭意指鋰石榴石之物理性存在大於50 wt.%。可由XRD測量相組分及彼等的濃度(wt.%)。於一些實例中，主相亦可由組成物中之鋰石榴石之物理性存在大於50 vol.%或大於50 mol.%，或類似者表示。
「微量相」、「第二相」，或類似術語或措辭意指組成物中之鋰枝晶生長抑制劑(即，晶粒邊界黏合增進劑)之物理性存在少於重量、體積、莫耳，或類似測量值之50%。於一些實例中，由XRD無法偵測之微量相，可由SEM測量以確認微量相之存在。
「SA」、「第二添加劑」、「第二相添加劑」、「第二相添加劑氧化物」、「相添加劑氧化物」、「添加劑氧化物」、「添加劑」，或類似術語意指，當包括於揭示之組成物中時，在主相內產生微量相或第二微量相之添加劑氧化物。
「LLZO」、「石榴石」，或類似術語意指化合物包含鋰(Li)、鑭(La)、鋯(Zr)，及氧(O)元素。任選地，摻雜劑元素可取代Li、La，或Zr之至少一者。
舉例來說，鋰-石榴石電解質包含下列之至少一者：(i) Li 7-3aLa 3Zr 2L aO 12，其中L=Al、Ga或Fe且0＜a＜0.33；(ii) Li 7La 3-bZr 2M bO 12，其中M=Bi、Ca，或Y且0＜b＜1；(iii) Li 7-cLa 3(Zr 2-c,N c)O 12，其中N=In、Si、Ge、Sn、V、W、Te、Nb，或Ta且0＜c＜1；(iv) Li 7-xLa 3(Zr 2-x, M x)O 12，其中M=In、Si、Ge、Sn、Sb、Sc、Ti、Hf、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y、Mg、Ca或彼等的組合且0＜x＜1，或彼等的組合。
「包括(include或includes)」或類似術語代表涵蓋但不限於，即，包括但不排除。
如本文中所使用的，術語「大約」、「約」、「實質上」，及類似術語意圖具有廣泛的含義，與此揭示所屬之主題之技術領域中具有通常知識者普遍接受的用法一致。閱讀此揭示之發明所屬技術領域中具有通常知識者應理解的是，這些術語旨在允許對所描述和請求的某些特徵進行描述，而不會將這些特徵的範圍限制在所提供的精確數字範圍內。因此，這些術語應被解釋為表明對所描述和請求的主題的非實質性或無關緊要的修飾或改變係視為在後附申請專利範圍中所記載的本發明的範疇內。
舉例來說，於修飾組成物中成分的數量、濃度、體積、製程溫度、製程時間、產量、流速、壓力、黏度等之值及其範圍，或組分的維度，和用於描述本揭示之實施例的類似值及其範圍時，「約」或類似術語意指可發生的數量變化，例如：經由用於製備材料、組成物、合成物、濃縮物、組成部分、製品，或使用配方之典型測量及處理程序；經由這些程序中非故意的錯誤；經由製造、來源，或是起始材料或用以進行方法之成分之純度中的差異；以及類似考量。術語「約」 (或類似術語)亦涵蓋由於具有特定初始濃度或混合物的組成物或配方老化而不同的量，以及由於混合或處理具有特定初始濃度或混合物的組成物或配方而不同的量。
如本文中所使用的，「任選的」、「任選地」，或類似者意圖代表接續地描述的事件或情況可能或不會發生，以及敘述包括其中事件或情況發生的例子以及其中事件或情況沒有發生的例子。如本文中所使用的，不定冠詞「一(a或an)」及其相應的定冠詞「該」代表至少一個，或一或更多個，除非另行指明。
如本文中所使用的，「室溫」或「RT」意圖代表於約18°C至25°C之範圍中的溫度。
本文中元件位置之參照(如，「頂」、「底」、「之上」、「之下」等等)僅用以描述附圖中各種元件的方位。應注意的是，根據其他例示性實施例，各種元件的方位可能不同，並且此等變化應由本揭示涵蓋。
可使用發明所屬技術領域中具有通常知識者熟知的縮寫(如，「h」或「hrs」代表小時、「g」或「gm」代表公克、「mL」代表毫升，及「RT」代表室溫、「nm」代表奈米，及類似縮寫)。
針對組分、成分、添加劑、尺寸、條件、時間，及類似態樣揭示之特定及較佳值，及彼等的範圍僅用於說明；彼等不排除其他定義值或是定義範圍內的其他值。此揭示之組成物、製品，及方法可包括如本文中所描述的任何值或值、特定值、更特定值，及較佳值的任何組合，包括明確的或隱含的中間值及範圍。
有關本文中之實質地任何複數和/或單數術語之使用，發明所屬技術領域中具有通常知識者可由複數轉換成單數和/或由單數轉換成複數，只要適於上下文和/或應用。為清楚之故，可在本文中明確提出各種單數/複數排列。
如同以上解釋的，基於Li-石榴石電解質(LLZO)之固態鋰電池經常遭受Li陽極和石榴石電解質間之不充分接觸之苦，其經常導致電池經歷低臨界電流密度(CCD)並且最終短路。解決此等問題之習知方式已包括：(A) H 3PO 4酸處理，以去除雜質同時形成Li 3PO 4之保護介層以及(B)利用SnO 2及MoS 2修飾電解質-陽極介面以形成Sn、Mo，及相關合金介層。然而，發現這些提案，隨電池循環，介層逐漸耗盡並造成最終電池失效。另外，這些介層不會增加電解質自身對鋰枝晶生長的抗性。
複合陶瓷電解質有效改進於主相晶粒邊界之黏合，從而藉由最小化鋰枝晶生長來改進CCD。臨界電流密度(CCD)意指於電解質中發生鋰枝晶穿透之前LLZO電解質可容許的最大電流密度，其影響電解質之枝晶抑制能力。藉由於LLZO燒結製程期間添加添加劑，添加劑或其分解產物於晶粒邊界聚集以增進晶粒邊界黏合及阻擋鋰枝晶生長。目前於研究添加劑之努力已包括(i)於LLZO中之LiOH•H 2O以形成Li 2CO 3及LiOH之微量相或(ii)添加Li 3PO 4至LLZO前驅物並藉由控制燒結條件允許Li 3PO 4於晶粒邊界維持微量相或(iii)添加LiAlO 2塗佈之LLZO顆粒以獲得Li-石榴石複合陶瓷電解質。然而，(i)至(iii)沒有一者能達到希望的CCD以符合實際應用的需求。
石榴石為用於Li-金屬電池技術之優勢固態電解質材料。相較目前於習知的Li離子電池中使用之碳陽極，Li金屬陽極允許遠遠較高的能量密度。於製造薄石榴石材料之方法中存在挑戰。舉例來說，一個挑戰為Li-枝晶形成，如同以上解釋的。第二個挑戰為薄膜所需強度，其由電池組件處理所決定。高強度希望的是細晶粒微結構。
本文中所揭示的為用於電解質應用、藉由添加金屬氧化物至具任選的元素摻雜(如，In、Si、Ge、Sn、Sb、Sc、Ti、Hf、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y、Ca等等之至少一者或彼等的組合)之LLZO而製備之Li-石榴石複合陶瓷薄膜。可使用元素摻雜劑以穩定LLZO成立方晶相。
Li金屬氧化物可用作用於晶粒邊界修飾之晶粒邊界材料，使得無或低Li離子導電材料可用以填充石榴石晶粒邊界，致使Li離子較佳地穿透石榴石晶粒，從而抑制Li-枝晶生長通過晶粒邊界並且抑制固態電解質臨界電流密度(CCD)。第二相材料之低熔化溫度亦幫助降低石榴石燒結溫度及增加晶粒黏合強度。
於一些實例中，Li-石榴石複合陶瓷可包含：鋰石榴石主相(如，如以上定義之LLZO)及鋰枝晶生長抑制劑微量相(如，如以上定義之SA)。於一些實例中，主相可摻雜有In、Si、Ge、Sn、Sb、Sc、Ti、Hf、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y、Mg、Ca之至少一者或彼等的組合以及微量相包含選自Li-矽酸鹽、Li-鎵酸鹽、Li-鋁酸鹽、Li-鎢酸鹽、Li-莫林那特、Li-Ta氧化物、Li-Nb-氧化物、Li-Sn-氧化物、Li-In-氧化物、Li-As-氧化物、Li-Sb-氧化物、Li-磷酸鹽或彼等的組合之群組的第二添加劑氧化物，基於陶瓷之總量以自＞0-10 wt.%存在。添加劑可改進陶瓷微結構之均勻性並且增進陶瓷之機械性能。如本文中所使用的「陶瓷微結構之均勻性」意指晶粒尺寸之分布。可最小化或消除對機械性能可具有不利影響之異常大晶粒發生，並且可達到細晶粒微結構。舉例來說，針對代表至少5%之總晶粒之晶粒群體進行測量之最大晶粒尺寸不應超過平均晶粒尺寸的多於20倍。
如本文中所揭示的，描述利用識別的複合組成物來製造緻密細晶粒金屬氧化物/石榴石複合薄膜結構之製程，相較於不包含金屬氧化物/石榴石複合薄膜之電池，識別的複合組成物造成具有改進的CCD之測試電池。
下述實例展現所揭示之陶瓷之製造、使用及分析。 實例
圖1說明根據一些實施例之用於製造金屬氧化物/LLZO複合薄膜之製程的流程圖。
實例1A—Li-石榴石複合陶瓷粉末之製備(石榴石粉末製造)
步驟1：第一混合步驟
於第一混合步驟中，石榴石氧化物化學式中且例如磨成細粉末之化學計量含量的無機材料混合在一起。無機材料可為碳酸鹽、磺酸鹽、硝酸鹽、草酸鹽、氫氧化物、氧化物，或彼等與化學式中其他元素之混合物。舉例來說，無機材料可為例如鋰化合物及至少一過渡金屬化合物(如，基於La、基於Zr等等)。於一些實施例中，無機材料化合物於化學式中亦可包含In、Si、Ge、Sn、Sb、Sc、Ti、Hf、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y、Mg、Ca之至少一者或彼等的組合。
於一些實施例中可能希望的是於起始無機批料中包括過量的鋰來源材料以補償自1000°C至1300°C (如，1100°C至1200°C)燒結/第二煅燒步驟之高溫期間的鋰損失。第一混合步驟可為乾混合製程(如，管式混合接續乾球研磨，或反之亦然)、乾研磨製程，或利用不會溶解無機材料之適當液體的濕研磨製程。可調整混合時間，諸如自數分鐘至數小時，例如根據觀察到之混合表現的規模或程度(如，1分鐘至48小時，或30分鐘至36小時，或1小時至24小時(如，12小時)，或本文中揭示之任何值或範圍)。藉由例如行星式軋機、磨碎機、球式混合、管式混合，或類似混合或研磨設備可完成研磨。
步驟2：第一煅燒步驟
於第一煅燒步驟中，於第一混合步驟之後，無機材料之混合物於例如自800°C至1200°C (如，950°C)，包括中間值及範圍，之預定溫度經煅燒，以反應及形成目標Li-石榴石。預定溫度取決於Li-石榴石的類型。煅燒時間例如自1小時至48小時(如，2小時至36小時，或3小時至24小時，或4小時至12小時(如，5小時)，或文中揭示之任何值或範圍)變化，並且亦取決於選擇之無機起始或來源批料的相對反應速率。於一些實例中，無關煅燒時間而選擇預定溫度，例如950°C持續5小時或1200°C持續5小時。於一些實施例中，於第一步驟中視需要，無機批料之預混物可經研磨接著煅燒(calcinated或calcined)。
步驟3：第二煅燒步驟
於第一煅燒步驟之後，無機材料之煅燒混合物可於較高的預定溫度經煅燒，預定溫度例如於自1000°C至1300°C (如，1200°C)，包括中間值及範圍，其中溫度上升速率(預-燒結)及冷卻速率(後-燒結)之範圍為自0.5°C/分鐘至10°C/分鐘(如，5°C/分鐘)。用於第二煅燒之預定溫度取決於Li-石榴石的種類。煅燒時間，例如自1小時至48小時(如，2小時至36小時，或3小時至24小時，或4小時至12小時(如，5小時)，或文中揭示之任何值或範圍)變化。
於一些實例中，步驟2及3可結合成具兩個保持階段(holding phase)的單一煅燒步驟(第一保持階段由步驟2代表及第二保持階段由步驟3代表)。
步驟4：研磨步驟
於第二煅燒步驟之後，藉由球式研磨和/或噴射研磨可研磨粉末，具90 wt.%之上述鋰石榴石立方晶相。當執行球式研磨時，經球式研磨的粉末較粗，具有介於1-5 µm之間之D50顆粒大小。當執行噴射研磨時，經噴射研磨之粉末較細緻，具有介於0.01-1 µm之間之D50顆粒大小。粗糙及細緻粉末兩者具有近似雙模顆粒大小分佈。針對薄帶鑄造，具有單模分佈之較細緻粉末較佳。
步驟5：篩分步驟
藉由通過100-沙礫之篩，步驟4之經研磨的粉末接著經過濾以獲得具有介於0.01-1 µm (如，0.6 µm)間之範圍之D50顆粒大小的最終Li-石榴石複合陶瓷粉末。當粉末形成為任意形狀，粉末可具有自0.01-1 µm之範圍的至少一尺寸。
實例1B
於實例1B中，分別使用0.5Ta-LLZO及Li 4.9La 3Zr 1.7W 0.3Ga 0.5O 12組成物石榴石於製造複合物。
藉由固態反應方法、使用Li 2CO 3、La 2O 3、ZrO 2及相應的摻雜劑氧化物(如，基於Ta者(如，Ta 2O 5)、基於W者(如，WO 3)，或基於Ga者(如，Ga 2O 3))作為前驅物來製備石榴石粉末。因為粉末吸收不同含量的被吸附物，於批量前使用TGA (RT-1000C)測量粉末(除Li 2CO 3外)，接著考量被吸附物之含量批量粉末含量。藉由管式混合接續球式混合徹底混合化學計量批量，及接著於具Pt覆蓋片之Pt坩堝中於具於950°C執行持續5小時之第一保持階段及於1200°C執行持續5小時之第二保持階段之單一煅燒步驟中進行加熱。於煅燒之後，大塊產物經噴射研磨接著以100-沙礫之篩進行篩分以獲得具約0.6 µm之D50的最終石榴石粉末。
圖2說明剛經噴射研磨之Ta-LLZO石榴石粉末的x光繞射(XRD)圖案，以確認組成物。
實例2—石榴石粉末鈍化
於一些實施例中，於粉漿(slip)製備(於以下更仔細描述)之前，於實例1A或1B中製備之石榴石粉末(如，Ta摻雜的LLZO，或類似地Ga和/或W摻雜的LLZO)可經空氣碳酸化或酸處理以鈍化其與其他薄帶鑄造粉漿組分之高反應性。此允許當薄帶鑄造粉漿時石榴石能夠穩定並因此最終生胚薄帶可為長時間穩定的。
藉由空氣碳酸化之石榴石粉末鈍化
將(實例1A或1B之)剛製造的石榴石粉末暴露至於50°C之空氣持續1個月。粉末與空氣中之H 2O及CO 2反應以形成H-LLZO (內核；H摻雜的LLZO)，具有覆蓋的Li 2CO 3外殼於石榴石粉末顆粒上。如同前述，此鈍化石榴石以防止當薄帶鑄造粉漿時石榴石與粉漿組成物中之有機組分反應。
藉由酸處理之石榴石粉末鈍化
於可供選擇的鈍化技術中，添加酸(如，HCl、HF、HNO 3、H 3PO 4、H 2SO 4、乙酸、硼酸、碳酸、檸檬酸、草酸等等)至(實例1A或1B之)剛製造之石榴石粉末的漿料。起初地，漿料的pH超過7，但藉由添加酸此值逐漸下降直到成為約6之希望的pH值。離心漿料以分離最終粉末。所獲得的測試粉末為以薄帶鑄造粉漿穩定之H-LLZO (質子化石榴石) (即沒有Li 2CO 3外殼形成—質子化石榴石的一個組成物)。
實例3—藉由添加Li金屬氧化物(LMO)前驅物之粉漿製造
於實施例中，藉由製造石榴石粉漿組成物開始薄帶鑄造製程。粉漿含有至少一種溶劑、有機黏合劑、增塑劑、鋰石榴石粉末、過量鋰來源、第二添加劑，及分散劑。典型的粉漿組成物配方列示於表1中，然而可變化鋰石榴石粉末、過量鋰來源、第二添加劑，及黏合劑的含量以達成各種高品質生胚薄帶。
組分 名稱 薄帶中Vol.% 粉漿中溶劑Vol.%
石榴石 Li-石榴石粉末 (來自實例2) 52.28  
過量Li來源 Li 2CO 3  
第二添加劑 M97E矽氧烷 石榴石之n% (可變的)  
分散劑  Disperbyk ®118 6.99  
溶劑 (1：1 wt.%) 丙酸正丁酯   65.55%
丙酸正丙酯
黏合劑 Elvacite 2046 27.93
增塑劑 鄰苯二甲酸二丁酯 12.80
表1
於一些實例中，粉漿組成物配方之分散劑可選自包含下列之群組：Disperbyk ®118、Disperbyk ®142、Disperbyk ®182、Disperbyk ®2022、Disperbyk ®2155、Solsperse TM41090、Anti-Terra ®250、魚油，或彼等的組合。於一些實例中，粉漿組成物配方之過量Li可選自包含下列之群組：Li 2CO 3、LiCl、LiNO 3、檸檬酸鋰、乙酸鋰、油酸鋰、LiF、Li 2SO 4，或彼等的組合。
粉漿製造包括於溶劑中分散鋰石榴石粉末、過量鋰來源，及第二添加劑之步驟以形成石榴石懸浮物。作為參考，添加Li 2CO 3作為過量鋰來源(Li前驅物)。於初始粉漿製造步驟中，含有50 wt.% SiO 2之M97E矽氧烷(Si前驅物)用作假性黏合劑/增塑劑(除了於生胚薄帶形成中添加的黏合劑及增塑劑)。於燒結期間，M97E矽氧烷可分解並且與Li 2CO 3反應以形成Li-矽酸鹽。類似地，針對包含基於鎢之化合物(如，WO 3)和/或基於鎵之化合物(如，Ga 2O 3)的第二添加劑之粉漿組成物配方，經由各自與Li 2CO 3之反應可分別地形成Li-鎢酸鹽及Li-鎵酸鹽。於一些實例中，可添加金屬氧化物或其他形式前驅物(如，WO 3、Ga 2O 3等等)至粉漿中作為第二添加劑，並薄帶鑄造成生胚薄帶。於燒結之步驟期間，這些金屬氧化物或前驅物與Li 2CO 3反應以分別地原位形成Li-鎢酸鹽、Li-鎵酸鹽等等。隨後，Li-矽酸鹽、Li-鎢酸鹽，和/或Li-鎵酸鹽之各者與鋰石榴石粉末於溶劑中混合以形成石榴石懸浮物。最終地，添加分散劑、黏合劑，及增塑劑至石榴石懸浮物，研磨(如，於2000 rpm磨碎研磨持續1-5小時(如，2小時))及於真空下除氣持續5至10分鐘。可於真空下執行研磨及混合並且冷卻以防止石榴石和其他粉漿組分之間之非預期反應。
實例4—薄帶鑄造
薄帶鑄造製程包括，例如粉漿製造(如上描述)、薄帶鑄造，及乾燥(燒結，如上描述)。使用例如6密耳至18密耳刮刀可執行薄帶鑄造。表1為可用於薄帶鑄造Li-矽酸鹽/石榴石複合生胚薄帶之粉漿組成物的實例。
具有及不具矽氧烷之生胚薄帶
表2顯示用於定性之實驗性薄帶鑄造條件之比較。來自表2之條件1-3的粉漿組成物藉由在惰性環境(N 2)中於950°C首先加熱持續2小時而經薄帶鑄造。於粉末冷卻後，隨即為薄帶鑄造。於表2中定性描述所得的生胚薄帶之穩定性。當薄帶變得易碎(即，脆性、破裂)，此表示其中含有的有機材料(黏合劑、增塑劑)衰減，其可能為與活化石榴石反應的結果。因此，於表2中，「可撓」可歸類為當生胚薄帶於90°彎曲且仍然不會破裂。
條件號碼 粉漿組成物 石榴石粉末鈍化? 生胚薄帶穩定性
1 表1，減掉矽氧烷 無 於＜1週易碎
2 表1 無 持續數月維持可撓
3 表1 實例2，藉由空氣碳酸化而鈍化 持續數月維持可撓
表2
實例5—薄帶燒結
石榴石薄帶於空氣及氬(Ar)氣氛兩者中經燒結。於燒結期間，生胚薄帶乘載於拖架上(如，氧化鋁、MgO、ZrO 2、石墨箔)或懸吊於空氣中。當使用拖架時，生胚石榴石薄帶可夾置於拖架片材之間以維持鋰。不需原生粉末(mother powder)。可使用兩個類型的燒結方法：習知燒結及快速燒結。於習知燒結中，溫度上升速率於100°C/小時至600°C/小時之範圍中。於快速燒結中，溫度上升速率於100°C/分鐘至1000°C/分鐘之範圍中。於快速燒結中之Li-損失明顯降低並因此生胚薄帶可於周圍空氣中經燒結而不需要任何覆蓋。為防止熱衝擊，托架較佳為薄膜形式(陶瓷薄片或陶瓷條帶)。針對習知燒結，以Ar或氮(N 2)氛圍為較佳。
矽氧烷 /Ga 及 W 摻雜的 LLZO 薄帶
於一個實例中，以0.5Ga-0.3W-LLZO石榴石、變化含量的矽氧烷(0 wt.%至10 wt.%之範圍中)，及70%過量Li (作為Li 2CO 3，相關石榴石中之Li含量)製備粉漿組成物以及薄帶鑄造。薄帶鑄造生胚薄帶於空氣中經燒結以450°C/分鐘之升溫速度至1000°C至1200°C之範圍中的溫度持續3分鐘。圖3A-3D說明石榴石薄帶(~70 µm)之截面掃描式電子顯微鏡(SEM)影像，包含：0 wt.%矽氧烷(即，無Li-矽酸鹽) (圖3A)、2 wt.%矽氧烷(圖3B)、5 wt.%矽氧烷(圖3C)，及10 wt.%矽氧烷(圖3D)，全部於1050°C/3分鐘經燒結。生胚薄帶含有70%過量鋰(Li)。10 wt.%矽氧烷樣本顯示稍微鬆散的晶粒結構。
圖4說明由感應耦合電漿(ICP)測量之於1050°C/3分鐘燒結之後，燒結的Ga-W-LLZO薄帶內之Li 2O wt.%相對矽石含量。當矽氧烷含量增加，例如自0 wt.%至2 wt.%至5 wt.%至10 wt.%，燒結的Ga-W-LLZO薄帶內之Li 2O wt.%也增加。如同以上解釋的，於燒結期間，矽氧烷分解並且與Li 2CO 3反應以形成Li-矽酸鹽。因此，由燒結的石榴石薄帶中保存作為Li-矽酸鹽之Li減緩Li損失，使得至少一些矽氧烷含量優於具0 wt.%矽氧烷之薄帶。
調查研究電氣性能，圖5說明於各種溫度燒結持續3分鐘且於彼等個別的生胚薄帶中包含不同含量矽氧烷之Ga-W-LLZO薄帶的Li離子導電率，如藉由使用金(Au)電極之電化學阻抗譜(EIS)所測量。當於晶粒邊界添加第二相時，預期Li離子導電率將嚴重降低。然而，不預期地，針對包含0 wt.%至5 wt.%之範圍中之矽氧烷含量的薄帶，Li離子導電率隨薄帶中之矽氧烷含量增加而增加，自1×10 -4至3.5×10 -4S/cm變化。Li離子導電率之此增加可能指示更多Li維持於樣本中，確認矽氧烷或Li-矽酸鹽有助於減少Li損失。不受理論所限制，針對較高程度的矽氧烷(如，10 wt.%)，於較低燒結溫度之較低導電率可能肇因於薄帶於燒結製程期間未充分緻密化。此指示(來自矽氧烷之)太高矽石含量增加石榴石之燒結溫度。因此，於矽氧烷含量大於10 wt.%時，燒結溫度可能變為非所欲的高。
於一些實例中，矽氧烷含量可存在於＞0 wt.%至10 wt.%，或＞0 wt.%至8 wt.%，或＞0 wt.%至5 wt.%，或5 wt.%至10 wt.%，或2 wt.%至10 wt.%之範圍，或其中揭示之任何值或子範圍。
表3描述XRD-測量之具有不同含量矽氧烷及於不同條件燒結(若未標記，表示薄帶經快速燒結)之薄石榴石燒結膜的相組成物。
Ga-W-LLZO + 矽氧烷含量 (wt.%) 燒結條件 相定量
0 1000°C/20分鐘 + 95°C/6小時(習知燒結) 94 wt.%立方晶石榴石 4 wt.% LiGaO 22 wt.% LaGaO 3
0 1050°C/3分鐘 95 wt.%立方晶石榴石 3 wt.% LiGaO 22 wt.% ZrO 2
5 1000°C/20分鐘 + 95°C/6小時(習知燒結) 94 wt.%立方晶石榴石 5 wt.% LiGaO 21 wt.% Li 4WO 5
5 1050°C/3分鐘 96 wt.%立方晶石榴石 3 wt.% LiGaO 21 wt.% Li 4WO 5
5 1100°C/5分鐘 95 wt.%立方晶石榴石 4 wt.% LiGaO 21 wt.% Li 2WO 4
5 1200°C/3分鐘 91 wt.%立方晶石榴石 6 wt.% LiGaO 22 wt.% ZrO 2Possible 1 wt.% Li 2WO 4
10 1000°C/3分鐘 93 wt.%立方晶石榴石 5 wt.% LiGaO 23 wt.% ZrO 2
10 1200°C/3分鐘 91 wt.%立方晶石榴石 3 wt.% LiGaO 24 wt.% La 2Zr 2O 72 wt.% ZrO 2
表3
所有樣本具有高濃度立方晶石榴石相(如，＞90 wt.%)。高立方晶相確保高離子導電率。LiGaO 2、LaGaO 3、La 2Zr 2O 7、Li 4WO 5、Li 2WO 4、ZrO 2等等的存在為Li-Ga、Si-W、Si-Zr等等之間之離子交換的副產品。副產品以及Li-矽酸鹽第二相留在晶粒邊界或三邊界點。因為Ga-W-LLZO組成物為低Li組成物並且因為系統含有高過量Li，石榴石於測試的燒製條件不會分解。
矽氧烷 /Ta 摻雜的 LLZO 薄帶
於一個實例中，以0.5Ta-LLZO石榴石、不同含量矽氧烷(於0 wt.%至10 wt.%之範圍中)，及15%或50%過量Li (作為Li 2CO 3，相關石榴石中之Li含量)製備粉漿組成物並且薄帶鑄造。薄帶鑄造生胚薄帶於空氣中經燒結，以450°C/分鐘之升溫速度至1000°C至1200°C之範圍中的溫度持續3分鐘。表4總結針對各種生胚薄帶組成物的燒結條件。
Ta-LLZO + 矽氧烷含量(wt.%) 過量Li含量(%) 燒結條件 微結構截面
0 15 1200°C/5分鐘 圖6A
2 圖6B
5 圖6C
8 圖6D
0 1200°C/10分鐘 圖7A
2 圖7B
5 圖7C
8 圖7D
0 50 1200°C/3分鐘 圖8A
5 圖8B
0 1200°C/15分鐘 圖9A
5 圖9B
表4
圖6A-9B說明包含不同含量矽氧烷添加劑及過量Li以及不同燒結條件之石榴石薄帶(~50 µm)的截面SEM影像。如同以上解釋的，至少一些矽氧烷含量優於具0 wt.%矽氧烷之薄帶以減緩Li損失。圖6A-9B證實過量Li含量及矽氧烷含量兩者影響薄帶燒結。舉例來說，針對具有15%過量Li含量之薄帶，具最低添加矽氧烷含量(2 wt.%)的那些例證最緻密微結構(圖6B及7B)而具最高添加矽氧烷含量(8 wt.%)的那些顯示最多孔結構(圖6D及7D)。由圖8A-9B，顯示過量Li (50%)過多造成不想要的鬆散晶粒連接(沿晶破壞)或於石榴石中異常及相對大的晶粒生長；細晶粒結構為高強度薄膜的必要條件。因為異常晶粒生長發生於高Li濃度，針對具有或不具有矽氧烷之樣本的SEM影像顯示具矽氧烷的樣本於燒結條件含有更多Li。換句話說，不僅是過量Li，而是矽氧烷的存在亦減緩Li損失，從而造成較高Li濃度。此結果再次強調添加矽氧烷的薄帶保留更多鋰。
以下表5提供Li 2O wt.%作為於1200°C燒結持續不同時間之後燒結的Ta-LLZO薄帶內之矽石含量的函數，如由感應耦合電漿(ICP)所測量。數據確認薄帶中之Li-矽酸鹽防止Li損失，尤其是針對接近化學計量Li 位準(如，11.1% Li 2O)之樣本。來自石榴石之Li損失較來自諸如Li 2CO 3、Li 2O、LiOH等等之過量Li物種困難。Li-矽酸鹽升高針對這些添加的過量Li物種之Li損失溫度並且於較高溫度保留更多過量Li。舉例來說，於2 wt.%矽氧烷薄帶中，僅1 wt.%為SiO 2。越多Li由此小量Li-矽酸鹽保持可能低於ICP偵測靈敏度。
Ta-LLZO + 矽氧烷含量(wt.%) 過量Li含量(%) 當於1200°C燒結持續3分鐘或5分鐘之Li 2O wt.% 當於1200°C燒結持續10分鐘或15分鐘之Li 2O wt.%
0 15 11.3 10.7
2 11.2 10.8
5 11.5 11.2
8 11.5 11.2
0 50 14.5 12.6
5 14.6 12.6
表5
圖10說明來自具有(5 wt.%矽氧烷)及不具矽氧烷添加劑於生胚薄帶中之石榴石薄膜的電化學阻抗譜(EIS)曲線(使用Au電極)。類似圖5之數據，兩個樣本均於1250°C/3分鐘經燒結，不預期地，兩個薄帶(包含0 wt.%或5 wt.%矽氧烷含量)具有相同之3×10 -4S/cm的Li離子導電率(如，於1×10 -4至3.5×10 -4S/cm之範圍內)，即便當於晶粒邊界添加第二相，預期Li離子導電率將嚴重降低。這些較高的導電率指示於升高的溫度(如，1250°C)足夠充分以形成緻密化薄膜。具有及不具有Li-矽酸鹽之相同Li離子導電率指示Li-矽酸鹽留在石榴石之三叉晶粒邊界。
Ta-LLZO + 矽氧烷含量(wt.%) 燒結條件 石榴石之晶格常數(Å) 相定量 立方晶石榴石
0 1200°C/5分鐘 12.9374 100 wt.%立方晶石榴石
0 1200°C/10分鐘 12.93412 100 wt.%立方晶石榴石
0 1250°C/5分鐘 12.93423 97.40 wt.%立方晶石榴石 2.60 wt.% La 2Zr 2O 7
0 1250°C/10分鐘 12.93354 85.40 wt.%立方晶石榴石 12.20 wt.% La 2Zr 2O 72.40 wt.% LaTaO 4
2 1200°C/10分鐘 12.93673 93.50 wt.%立方晶石榴石 5.20 wt.% La 2Zr 2O 71.30 wt.% LaTaO 4
5 1200°C/5分鐘 12.93632 100 wt.%立方晶石榴石
5 1200°C/10分鐘 12.93708 100 wt.%立方晶石榴石
5 1250°C/5分鐘 12.93509 93.30 wt.%立方晶石榴石 5.60 wt.% La 2Zr 2O 71.10 wt.% LaTaO 4
5 1250°C/10分鐘 12.93581 100 wt.%立方晶石榴石
8 1200°C/10分鐘 12.93635 98.80 wt.%立方晶石榴石 1.20 wt.% La 2Zr 2O 7
表6
表6揭露燒結的Li-矽酸鹽/Ta-LLZO薄帶及純Ta-LLZO薄帶之XRD測量的相組成物。多數樣本具有超過93 wt.%立方晶石榴石之高濃度立方晶石榴石相。高立方晶相確保高離子導電率。La 2Zr 2O 7及LaTaO 4之存在為石榴石分解之副產品。這些不同於Li-矽酸鹽第二相，其留在晶粒邊界或三邊界點。這些副產品呈大團塊(數倍石榴石晶粒大小)及於燒結的薄帶中之孔洞。過量的副產品導致導電率下降並減弱薄帶強度。舉例來說，針對不具Li-矽酸鹽在較高溫度燒製較長時段的樣本，薄帶損失過多Li，造成立方晶石榴石相降低至85.4 wt.%。於是，副產品增多亦增加。由於Li-矽酸鹽降低Li損失，具有Li-矽酸鹽之樣本可維持彼等之100 wt.%立方晶相。此外，具有(2 wt.%至8 wt.%)及不具(0 wt.%)Li-矽酸鹽之樣本具有大約相同的晶格常數，指示Si未摻雜至石榴石晶格中以及Li-矽酸鹽留在晶粒邊界或三邊界點。
實例6—燒結製程之比較
習知燒結涉及1-10°C/分鐘(60-600°C/小時)之加熱和/或冷卻升降溫速率，而於本案中描述之燒結製程(即，「快速燒製」)涉及100-600°C/分鐘之加熱和/或冷卻升降溫速率。
如同本文中所揭示的，藉由添加過量Li (如，呈Li 2CO 3形式)至生胚薄帶中來形成薄石榴石薄帶來補償燒結期間之Li損失以獲得具高立方晶石榴石相濃度(接近100%)之緻密燒結結構(即，相對密度＞98%)。藉由縮短溫度上升時間，快速燒製抑制Li損失(當溫度大於900°C時Li損失顯著)，其使得能於較困難條件燒結石榴石薄帶。Li損失充分地降低，生胚薄帶中所需的過量Li亦可降低。舉例來說，於厚度約100µm之0.5Ta-LLZO生胚薄帶中，(A)當於氬中燒製時，於快速燒製中僅需5-10%過量Li而於習知燒結中需要超過20%的過量Li；或是(B)當於周圍空氣中燒製時，於快速燒製中僅需約15-20%過量Li而於習知燒結中需要超過50%的過量Li。
實例7–定性技術
形態及相分析
藉由掃描式電子顯微鏡(JEOL, JSM-6010PLUS/LA)獲得掃描式電子顯微鏡(SEM)影像。藉由於室溫在10–80°之2θ範圍中之x光粉末繞射(Bruker, D4, Cu-Kα radiation, λ=1.5415Å)獲得X光粉末繞射(XRD)圖案。使用HF/HClO4發煙程序(發煙至乾燥兩次)執行感應耦合電漿(ICP)測量，接著將殘餘物溶解於HCl中。使用Perkin Elmer PinnAAcle 500執行Li分析。
電化學阻抗譜 (EIS)
藉由AC阻抗分析(Solartron SI 1287)以0.1Hz至1MHz之範圍的頻率測量EIS。
因此，如本文中呈現的，此揭示關於用於固態鋰金屬電池應用中之Li-石榴石電解質之增進的晶粒邊界黏合之改進的鋰-石榴石複合陶瓷電解質。增進的晶粒邊界組成物有助於抵擋有害的Li-枝晶生長。
具體地，本案揭示包含鋰石榴石立方晶主相(如，LLZO，如以上定義者)及鋰枝晶生長抑制劑微量相(如，SA，如以上定義者)之Li-石榴石複合陶瓷。於一些實例中，主相可摻雜有In、Si、Ge、Sn、Sb、Sc、Ti、Hf、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y、Mg、Ca之至少一者或彼等的組合以及微量相包含選自下列群組之第二添加劑氧化物：Li-矽酸鹽、Li-鎵酸鹽、Li-鋁酸鹽、Li-鎢酸鹽、Li-莫林那特、Li-Ta氧化物、Li-Nb-氧化物、Li-Sn-氧化物、Li-In-氧化物、Li-As-氧化物、Li-Sb-氧化物、Li-磷酸鹽或彼等的組合，基於陶瓷總量以自＞0-10 wt.%存在。添加劑可改進陶瓷微結構之均勻性並且增進陶瓷之機械性能。因為具有及不具第二相之樣本具有類似的晶格常數，此指示第二(即，微量)相(如，Li-矽酸鹽)保持於晶粒邊界或三邊界點並且沒有被引入Li-石榴石中。
本案亦揭示製造具緻密結構、高立方晶相及高Li離子導電率之Li金屬氧化物/石榴石複合物之薄膜的製程。製程包括(1)Li-石榴石複合陶瓷粉末之製備；(2)石榴石粉末鈍化；(3)藉由添加Li金屬氧化物(LMO)前驅物之粉漿製造；(4)薄帶鑄造；以及(5)快速燒製薄帶燒結生胚薄帶成為緻密薄帶。生胚薄帶中之Li 2CO 3用作Li來源以補償燒結期間之Li損失。於高溫亦可產生增進燒結之液體相。於1000°C-1300°C範圍之溫度執行複合石榴石薄帶燒結持續數分鐘。本文中所揭示的製程允許大規模燒結薄帶，具大幅改進的密度。
燒結的石榴石薄膜具有高Li離子導電率(＞10 -4S/cm)、自30-150 µm之厚度，及相對密度為＞95%。
優點包括：(1)於生胚薄帶中添加矽氧烷延長生胚薄帶壽命(不添加矽氧烷、非鈍化石榴石粉末澆鑄的薄帶於1-2週內變脆；添加矽氧烷，石榴石薄帶可維持數個月)；(2)添加矽氧烷及Li 2CO 3使得於燒結期間形成Li-矽酸鹽；(3)石榴石與Li-矽酸鹽穩定；(4) Li-矽酸鹽非Li離子導電且可用以阻擋石榴石中之Li-枝晶生長；(5) Li-矽酸鹽幫助降低燒結期間之Li損失；以及(6)於石榴石晶粒邊界之其他Li金屬氧化物，諸如Li-鎵酸鹽、Li-鋁酸鹽、Li-鎢酸鹽、Li-莫林那特、Li-Ta氧化物、Li-Nb-氧化物、Li-Sn-氧化物、Li-In-氧化物、Li-As-氧化物、Li-Sb-氧化物、Li-磷酸鹽或彼等的組合亦可阻擋Li-枝晶穿透通過晶粒邊界。
對發明所屬技術領域中具有通常知識者為顯而易見的是，可進行各種修飾及變化而不背離請求之主題的精神或範疇。因此，請求之主題不受到限制，除非根據後附的申請專利範圍及其等效物。
無
由以下之實施方式，連同附圖，將更全面地理解此揭示，於圖式中：
圖1說明根據一些實施例之用於製造Li-金屬-氧化物/LLZO複合薄膜之製程的流程圖。
圖2說明根據一些實施例之剛經噴射研磨之Ta-LLZO石榴石粉末的x光繞射(XRD)圖案。
圖3A-3D說明根據一些實施例之石榴石薄帶之截面掃描式電子顯微鏡(SEM)影像，石榴石薄帶包含：0 wt.%之矽氧烷(圖3A)、2 wt.%之矽氧烷(圖3B)、5 wt.%之矽氧烷(圖3C)，及10 wt.%之矽氧烷(圖3D)，全部於1050°C/3分鐘經燒結。生胚薄帶含有70%過量鋰(Li)。
圖4說明根據一些實施例之於1050°C/3分鐘燒結之後，經燒結的Ga-W-LLZO薄帶內之Li 2O wt.%相對矽石含量。
圖5說明根據一些實施例之於各種溫度燒結持續3分鐘及於彼等個別生胚薄帶中包含不同含量之矽氧烷之Ga-W-LLZO薄帶的Li離子導電率。
圖6A-6D說明根據一些實施例之於1200°C/5分鐘經燒結之包含不同含量之過量Li及矽氧烷添加劑之石榴石薄帶的截面SEM影像。
圖7A-7D說明根據一些實施例之於1200°C/10分鐘經燒結之包含不同含量之過量Li及矽氧烷添加劑之石榴石薄帶的截面SEM影像。
圖8A及8B說明根據一些實施例之於1200°C/3分鐘經燒結之包含不同含量之過量Li及矽氧烷添加劑之石榴石薄帶的截面SEM影像。
圖9A及9B說明說明根據一些實施例之於1200°C/15分鐘經燒結之包含不同含量之過量Li及矽氧烷添加劑之石榴石薄帶的截面SEM影像。
圖10說明根據一些實施例之來自生胚薄帶中具及不具矽氧烷添加劑之石榴石薄膜的電化學阻抗譜(EIS)曲線。
國內寄存資訊(請依寄存機構、日期、號碼順序註記) 無 國外寄存資訊(請依寄存國家、機構、日期、號碼順序註記) 無

Claims (22)

  1. 一種燒結複合陶瓷，包含： 一鋰-石榴石主相；以及 一鋰枝晶生長抑制劑微量相， 其中該鋰枝晶生長抑制劑微量相包含，基於該燒結複合陶瓷之總重量，於＞0-10 wt.%之一範圍中之一Li金屬氧化物。
  2. 如請求項1所述之燒結複合陶瓷，其中該鋰-石榴石主相包含下列之至少一者： (i) Li 7-3aLa 3Zr 2L aO 12，其中L=Al、Ga或Fe以及0＜a＜0.33； (ii) Li 7La 3-bZr 2M bO 12，其中M=Bi、Ca或Y以及0＜b＜1； (iii) Li 7-cLa 3(Zr 2-c, N c)O 12，其中N=In、Si、Ge、Sn、Sb、Sc、Ti、Hf、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y、Mg、Ca或彼等的組合以及0＜c＜1， 或彼等的一組合。
  3. 如請求項2所述之燒結複合陶瓷，其中該鋰-石榴石主相包含： Li 7-cLa 3(Zr 2-c, N c)O 12，其中N=Ta、Ga、W或彼等的組合，以及0＜c＜1。
  4. 如請求項1-3之任一項所述之燒結複合陶瓷，其中該Li金屬氧化物包含：Li-矽酸鹽、Li-鎵酸鹽、Li-鋁酸鹽、Li-鎢酸鹽、Li-莫林那特、Li-Ta氧化物、Li-Nb-氧化物、Li-Sn-氧化物、Li-In-氧化物、Li-As-氧化物、Li-Sb-氧化物、Li-磷酸鹽，或彼等的組合。
  5. 如請求項4所述之燒結複合陶瓷，其中該金屬氧化物包含Li-矽酸鹽。
  6. 如請求項1-3之任一項所述之燒結複合陶瓷，其中該鋰-石榴石主相包含至少90 wt.%之一鋰石榴石立方晶相。
  7. 如請求項1-3之任一項所述之燒結複合陶瓷，其中針對代表至少5%之一總晶粒群體之一晶粒群體所測量之一最大晶粒尺寸不超過該總晶粒群體之一平均晶粒尺寸的多於20倍。
  8. 如請求項1-3之任一項所述之燒結複合陶瓷，包含具有於30-150 µm之一範圍中之一厚度的一薄膜。
  9. 如請求項8所述之燒結複合陶瓷，其中該薄膜具有至少10 -4S/cm之一Li離子導電率以及該薄膜之一理論最大密度之至少90%之一相對密度。
  10. 一種電池，包含： 至少一個鋰電極；以及 一電解質，接觸該至少一個鋰電極， 其中該電解質為一鋰-石榴石複合電解質，包含如請求項1-3之任一項所述之燒結複合陶瓷。
  11. 一種燒結複合陶瓷，包含： 一鋰-石榴石主相；以及 一鋰枝晶生長抑制劑微量相， 其中： 該鋰-石榴石主相包含： Li 7-cLa 3(Zr 2-c, N c)O 12，其中N=Ta、Ga、W或彼等的組合，以及0＜c＜1，以及 該鋰枝晶生長抑制劑微量相包含，基於該燒結複合陶瓷之總重量，於＞0-10 wt.%之一範圍中之Li-矽酸鹽。
  12. 如請求項11所述之燒結複合陶瓷，其中該鋰-石榴石主相包含至少90 wt.%之一鋰石榴石立方晶相。
  13. 如請求項11或請求項12所述之燒結複合陶瓷，其中針對代表至少5%之一總晶粒群體之一晶粒群體所測量之一最大晶粒尺寸不超過該總晶粒群體之一平均晶粒尺寸的多於20倍。
  14. 如請求項11或請求項12所述之燒結複合陶瓷，包含具有於30-150 µm之一範圍中之一厚度的一薄膜。
  15. 一種燒結複合陶瓷，包含： 一鋰-石榴石主相；以及 一鋰枝晶生長抑制劑微量相， 其中該燒結複合陶瓷包含下列之至少一者： 至少10 -4S/cm之一Li離子導電率；以及 該薄膜之一理論最大密度之至少90%之一相對密度。
  16. 一種方法，包含以下步驟： 於950°C至1500°C之一範圍中之一溫度燒結一金屬氧化物組分/石榴石生胚薄帶以形成一複合陶瓷，該複合陶瓷包含： 一鋰-石榴石主相；以及 一鋰枝晶生長抑制劑微量相， 其中該鋰枝晶生長抑制劑微量相包含，基於該燒結複合陶瓷之總重量，於＞0-10 wt.%之一範圍中之一Li金屬氧化物。
  17. 如請求項16所述之方法，其中該燒結步驟包含以下步驟： 自室溫加熱至該溫度範圍； 保持於該溫度範圍持續1-20分鐘之範圍中之一時段； 自該溫度範圍冷卻至室溫， 其中： 用於該加熱步驟之一升溫速率(HRR)為100°C/分鐘＜HRR＜1000°C/分鐘，以及 用於該冷卻步驟之一冷卻速率(CR)為100°C/分鐘＜CR＜1000°C/分鐘。
  18. 如請求項17所述之方法，其中： 該HRR為250°C/分鐘＜HRR＜750°C/分鐘， 該CR為250°C/分鐘＜CR＜750°C/分鐘，以及 該溫度範圍為1100°C至1300°C。
  19. 如請求項16所述之方法，其中該燒結複合陶瓷包含下列之至少一者： 至少10 -4S/cm之一Li離子導電率；以及 該薄膜之一理論最大密度之至少90%之一相對密度。
  20. 如請求項16-19之任一項所述之方法，其中該金屬氧化物組分/石榴石生胚薄帶係藉由下列步驟形成： 使一過量Li來源與一添加劑反應以形成一Li金屬氧化物(LMO)前驅物； 使該LMO前驅物與一鈍化石榴石粉末混合以形成一石榴石懸浮物； 添加分散劑、黏合劑，及增塑劑至該石榴石懸浮物以形成一粉漿組成物；以及 薄帶鑄造該粉漿組成物。
  21. 如請求項20所述之方法，其中該添加劑包含下列之至少一者：矽氧烷、三氧化鎢(WO 3)，及氧化鎵(Ga 2O 3)。
  22. 如請求項16-19之任一項所述之方法，其中該金屬氧化物組分/石榴石生胚薄帶係藉由下列步驟形成： 混合一過量Li來源、一Li金屬氧化物(LMO)前驅物，及一鈍化石榴石粉末以形成一石榴石懸浮物； 添加分散劑、黏合劑，及增塑劑至該石榴石懸浮物以形成一粉漿組成物；以及 薄帶鑄造該粉漿組成物。
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