TWI434452B - 具有石榴石結構之離子導體 - Google Patents

具有石榴石結構之離子導體 Download PDF

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TWI434452B
TWI434452B TW097124935A TW97124935A TWI434452B TW I434452 B TWI434452 B TW I434452B TW 097124935 A TW097124935 A TW 097124935A TW 97124935 A TW97124935 A TW 97124935A TW I434452 B TWI434452 B TW I434452B
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solid
ionic conductor
garnet
conductivity
hours
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TW200910671A (en
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Werner Weppner
Ramaswamy Murugan
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Basf Se
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Description

具有石榴石結構之離子導體
本發明係關於具有石榴石樣結構之化學性穩定的固態離子導體在電池、超級電容器、蓄電池及電致變色裝置、化學感測器及熱電轉換器中的用途，以及適用於該等用途的新穎化合物。
可再充電(二次)電池係在電氣設備及電子設備需要或至少部分時間需要獨立於電網而操作的情況下使用。在此背景下，針對此使用形式對作為電解質材料的固態離子導體進行研究為當前材料研究之一重要方面。電池僅由固體組成的優點在於確保無滲漏、小型化、電化學穩定性、相對較高的能量密度及相對較長的壽命。
在各種電池技術中，基於鋰離子的電池系統近年來變得日益完善。其尤其以其可達成的高電能密度及功率而著名，此可歸因於鋰離子之高化學反應性及低質量以及其高遷移率。固態鋰離子導體之開發近年來已頗引人注意。實例為Li2.9 PO3.3 N0.46 或Li3 N及Li-β-氧化鋁。然而，Li2.9 PO3.3 N0.46 具有比液態電解質顯著更低的離子電導率。Li3 N及Li-β-氧化鋁對於濕氣很敏感。此外，Li3 N在室溫下、在低至0.445V的電壓下分解，且Li-β-氧化鋁化學性不穩定性。
具有石榴石樣結構的鋰離子導體首次描述於Thangadurai等人之研究中，"Novel Fast Lithium Ion Conduction in Garnet-Type Li5 La3 M2 O12 (M=Nb, Ta)", J. Am. Ceram. Soc. 86, 437-440, 2003。石榴石樣Li5 La3 M2 O12 化合物具有明顯的鋰離子電導率。
就結構而言，石榴石為以立方晶系結晶、具有一般組成X3 Y2 (SiO4 )3 之正矽酸鹽，其中X及Y為八配位及六配位陽離子位點。個別SiO4 四面體彼此間經由填隙式B陽離子藉由離子鍵相連。
與理想的石榴石結構相比，Thangadurai等人之上述研究中所述之式Li5 La3 M2 O12 (M=Nb、Ta)之石榴石樣化合物含有過量的Li離子。La3+ 及M5+ 離子佔據八配位及六配位位點，而鋰離子佔據具有六配位的位置。
PCT申請案WO 2005/085138報導，其他石榴石樣鋰離子導體在形式上係由式Li5 La3 M2 O12 (其中M=Nb或Ta)之化合物藉由異價取代獲得。La3+ 位點之異價取代可增強網路連接性，且使得能夠修改可用之空位數。電荷平衡較佳經由Li+ 離子(L)達成。為本發明之目的，"異價取代"意謂，作為形成陽離子空位、陰離子空位、填隙式陽離子及/或填隙式陰離子的結果，離子被具有不同氧化態的離子置換。固態鋰離子導體具有化學穩定性，且具有3.4×10-6 S/cm之離子電導率。由於其離子電導率高，同時電子電導率可忽略不計，因此其可用作固態電解質。
WO 2005/085138中所述的化合物一般具有化學計量組成L5+x Ay Gz M2 O12 ，其中：L在各種情況下獨立地為任何較佳單價陽離子；A在各種情況下獨立地為單價、二價、三價或四價陽離 子；G在各種情況下獨立地為單價、二價、三價或四價陽離子；M在各種情況下獨立地為三價、四價或五價陽離子；0<x3，0y3，0z3；且O可部分或完全地經二價及/或三價陰離子(諸如N3- )置換。
在所述離子導體中，M在各種情況下為金屬Nb與Ta中之一者。未給出金屬離子之其他實例。經由鋰離子(L=Li)發生離子導電。
具有石榴石結構的鋰離子導體之其他實例近年來已經檢證(V. Thangadurai, W. Weppner,Adv. Funct. Mater . 2005, 15, 107-112; V. Thangadurai, W. Weppner,J. Power Sources, 2005, 142, 339-344)。此處，Li6 BaLa2 Ta2 O12 在22℃下具有4×10-5 Scm-1 之最高Li+ 離子電導率，活化能為0.40 eV。雖然Li6 BaLa2 Ta2 O12 對與金屬鋰、濕氣、空氣及常用電極材料的反應具有穩定性，但在室溫下，體積電導率及總電導率仍不夠高至使得能夠開發理想的可再充電固態鋰離子電池。
與先前技術之上述離子導體相關聯的另一問題為，所提議之金屬鈮及鉭相對較貴且不易獲得。此外，使用完全由所述石榴石樣化合物組成的固體電解質複雜且成本高。
因此，本發明之一目標為提供其中至少部分克服上述缺陷之經改良之固態離子導體。
根據本發明，現已發現鋯可用作石榴石樣離子導體中之金屬M。與鈮及鉭相比，鋯易獲得且形成很穩定的固態結構。雖然Nb及Ta形式上以氧化態+V存在於石榴石結構中，但Zr較佳呈氧化態+IV。
因此，本發明在一實施例中提供具有石榴石樣晶體結構且具有化學計量組成L7+x Ax G3-x Zr2 O12 的固態離子導體，其中L在各種情況下獨立地為單價陽離子；A在各種情況下獨立地為二價陽離子；G在各種情況下獨立地為三價陽離子；0x3；且O可部分或完全地經二價及/或三價陰離子(諸如N3- )置換。
L尤其較佳地為鹼金屬離子，例如Li+ 、Na+ 或K+ 。詳言之，L亦可為各種鹼金屬離子之組合。在本發明之一尤其較佳實施例中，L=Na+ 。鈉非常低廉且可以任意量獲得。小的Na+ 離子在石榴石樣結構中易移動，且可與鋯組合而給出化學性穩定的晶體結構。
A為任何二價陽離子或該等陽離子之任何組合。A較佳可使用二價金屬陽離子。鹼土金屬離子(諸如Ca、Sr、Ba及/或Mg)以及二價過渡金屬陽離子(諸如Zn)尤其較佳。已發現該等離子在本發明之石榴石樣化合物中移動很小(即使有的話)，因此離子導電實質上經由L發生。
在上述組成中，0x2亦較佳且0x1尤其較佳。 在本發明之一實施例中，x=0，因此A不存在於石榴石樣化合物中。
G為任何三價陽離子或該等陽離子之任何組合。G較佳可使用三價金屬陽離子。G=La尤其較佳。
在具有上述組成之結構中，O2- 可部分或完全地經其他陰離子置換。舉例而言，用其他二價陰離子將O2- 完全或部分地置換為有利的。此外，O2- 亦可在適當的電荷補償下經三價陰離子異價置換。
在另一態樣中，本發明提供具有化學計量組成L7+x Ax La3-x Zr2 O12 之固態離子導體，其中A為二價金屬且L為Li或Na。Na因其易得性而尤其較佳。在一較佳實施例中，x=0，因此組成為L7 La3 Zr2 O12 。
A較佳選自鹼土金屬，較佳Ca、Sr、Ba及/或Mg。A選自二價過渡金屬亦較佳，例如A=Zn。A=Sr或Ba最佳。
具有組成L7+x Ax La3-x Zr2 O12 之離子導體具有石榴石樣晶體結構。與具有組成L5 La3 Nb2 O12 (L=Li)之已知化合物相比，該兩個Nb(+V)陽離子形式上已經兩個Zr(+IV)陽離子及兩個單價L陽離子置換。此外，La(+III)可經A(+II)及L(+I)置換。以此方式，該結構中之L之總比例已增大。L較佳為Li或Na，具有石榴石結構之化合物經由其發生離子導電。因此，本發明之化合物使提供顯著改良之離子導體成為可能。
與先前技術之化合物相比，具有組成L7+x Ax La3-x Zr2 O12 之材料呈現增大的離子電導率。由於本發明之化合物之石 榴石結構為三維各向同性結構，因此離子導電在三維進行而無優先方向係可能的。
另一方面，本發明之化合物之電子電導率相對較低。本發明之化合物之多晶樣本亦具有低晶界電阻，以使得總電導率實質上完全由體積電導率構成。
該等材料之另一優點為其化學穩定性高。詳言之，該等材料在與熔融鋰接觸加熱時不呈現可辨識的變化。在高達350℃的溫度及高達6 V的直流電壓下，未觀測到化學分解。
具有石榴石結構之本發明之尤其較佳化合物之一實例為Li7 La3 Zr2 O12 。高的鋰離子電導率、良好熱穩定性及化學穩定性(就與可能電極之反應而言)、環境相容性、原料之可取得性、低製造成本及簡單生產及密封性使得Li7 La3 Zr2 O12 成為尤其適用於可再充電鋰離子電池的有前景之固體電解質。
根據另一態樣，本發明提供一種製備具有石榴石樣結構之固態離子導體的方法。該等化合物可藉由所存在元素之適當鹽及/或氧化物之反應(例如經由固態反應)形成。特別有用的原料為在反應過程中轉化為相應氧化物的硝酸鹽、碳酸鹽及氫氧化物。
更特定而言，本發明係關於一種製備具有組成L7+x Ax G3-x Zr2 O12 (例如Na6 ALa2 Zr2 O12 )之固態離子導體的方法。該等材料可藉由A、G及Zr之適當鹽及/或氧化物與L之氫氧化物、硝酸鹽或碳酸鹽以固態反應方式進行反應來獲得。A係如上所 定義。二價金屬A較佳以硝酸鹽之形式使用。此處，較佳為Ca(NO3 )2 、Sr(NO3 )2 及Ba(NO3 )2 。在G之情況下，較佳使用La，La較佳以La2 O3 之形式使用。Zr以氧化物(較佳ZrO2 )之形式使用有利。L較佳以LOH、LNO3 或L2 CO3 之形式使用。舉例而言，較佳可使用LiOH．H2 O或NaOH．H2 O。為在樣本之熱處理期間補償L(例如L=Li、Na)之重量損失，較佳使用過量(例如過量10 wt%)的各別鹽。
在第一步驟中將原料混合，且(例如)可在使用氧化鋯研磨介質的球磨中於2-丙醇中研磨。隨後將以此方式獲得的混合物在空氣中在較佳400-1000℃範圍內之溫度下加熱數小時，較佳2-10小時。600-800℃之溫度(例如約700℃)及4-8小時之熱處理時間(例如約6小時)特別適宜。接著再次進行研磨，較佳亦在使用氧化鋯研磨介質的球磨中於2-丙醇中進行研磨。隨後將反應產物單向或較佳均衡施壓以獲得成形件，例如片粒。接著將該等成形件在較佳700-1200℃、更佳800-1000℃範圍內的溫度下燒結數小時，較佳10-50小時，更佳20-30小時。此處，約900℃之溫度及約24小時之熱處理時間特別適宜。在此燒結過程中，為避免L氧化物之過多損耗，用具有相同組成之粉末覆蓋樣本係有利的。
由於全部組分皆存在可溶性鹽，因此易用於製備化合物的可能方法為前驅物方法(例如，Pecchini方法)、甘胺酸方法或沈澱反應法。
本發明之固態離子導體(例如，鋰或鈉離子導體)作為固 態電解質為一種寶貴的原料。由於該等材料具有非常高的離子電導率，同時電子傳導可忽略不計，因此其可用作具有很高能量密度之電池(例如鋰或鈉電池)之固體電解質。該等材料之高穩定性(就例如與元素鋰及常用電極材料之化學反應而言)促使(例如)本發明之固態離子導體能夠實際使用於電池中。
與常用固體電解質材料相比，本發明之固體電解質與電極之間之相界電阻亦極小。因此，具有相對較高功率(高電流)的電池可使用本發明之材料製造。與使用液態電解質相比，使用本發明之固態電解質亦導致改良之安全性。當機動車輛中使用該等電解質時，此特別有利。
在另一態樣中，除用於電池外，本發明亦提供該等固態離子導體(例如鋰離子導體)在電致變色系統(視窗、VDU、外牆等)中的用途及在超級電容器用於瞬時能量儲存與釋放的用途。使用本發明之離子導體時，可達成100 F/cm3 或100 F/cm3 以上之電容器能量密度。本發明之另一態樣為石榴石樣固態離子導體用作感測器、尤其多種氣體感測器的用途。根據本發明，亦可將該材料用於使熱有效地直接轉換為電能的熱電轉換器中。
具有石榴石樣結構的離子導體亦可與其他電解質(例如習知的非質子性液態電解質)組合用作緩衝層。因此，無需使用完全由石榴石樣結構組成的電解質。相反，可將任何已知的電解質(例如，可以液體、凝膠或固體形式存在的電解質)與新穎的石榴石樣離子導體組合使用。
因此，本發明在另一態樣中提供具有石榴石樣晶體結構之固態離子導體用作電極前之保護層以便改良針對電解質之化學穩定性的用途。為此目的，不僅可使用本發明之含鋯石榴石樣結構，而且可使用(例如)WO 2005/085138中所述的石榴石樣化合物。使用離子導體作為電極前之緩衝結構可防止短路，且使得有可能產生並施加相對較高電壓以便達成顯著更大的能量密度及壽命。
以下實例用於說明本發明之特別較佳實施例。
實例：
化學計量量之在各種情況下皆高度純之原料：在200℃下預乾燥6小時、過量10 wt%以補償燒結過程中之Li損失的LiOH(Alfa Aesar, >99%)；在900℃預乾燥24小時的La2 O3 (Alfa Aesar,>99.99%)；及ZrO2 (Aldrich,>99%)皆以固態反應方式進行反應。
使用氧化鋯容器及磨球將原料於2-丙醇中球磨約12小時。之後，在900℃及1125℃下、在空氣中熱處理12小時。接著將所得產物再次球磨。隨後對反應產物均衡施壓以形成片粒並在1230℃下燒結36小時。在此程序期間將樣本用具有相同組成的粉末覆蓋，以免鋰過多損耗。所有處理中的加熱速率為每分鐘1℃。將經燒結的壓片經由金剛石鋸切成更薄的片粒。使用X射線粉末繞射術(XRD)(SEIFERT 3000, CuKα , Germany)監測相形成。依據粉末 XRD資料、使用最小二乘法測定晶格常數。
在空氣中，使用不同厚度的兩個片粒(厚片：1.02cm厚且直徑0.92cm；及薄片：0.18cm厚且直徑0.98cm)進行電導率之量測。使用Li離子阻斷性Au電極(在700℃下固化1小時而得的Au膏)在18至350℃的溫度範圍內、經由阻抗與增益相位分析儀(HP 4192 A, Hewlett-Packard Co., Palo Alto, CA)(5 Hz-13 MHz)進行量測。每次量測阻抗之前，使樣本在恆溫下均衡3至6小時。每個片粒以兩個連續加熱與冷卻循環進行阻抗量測。在空氣中、在29-900-20℃之溫度範圍內、在每分鐘2℃之加熱速率及冷卻速率下量測且在900℃下以等溫方式量測熱解重量分析(TGA)及差熱分析(NETZSCH STA 409 C/CD)之資料。
在充氬手套工作箱中、藉由使片粒與大量過剩的熔融鋰在鉬坩堝中反應48小時來檢查Li7 La3 Zr2 O12 對熔融鋰的穩定性。
儘管已對Li5 La3 M2 O12 (M=Nb、Ta)石榴石進行過很多X-射線繞射(XRD)研究，但在鋰陽離子之空間群及位置方面，尚存在關於結構的爭議(a)D. Mazza, Mater. Lett. 1988, 7, 205-207; b)H. Hyooma, K. Hayashi, Mater. Res. Bull. 1988, 23, 1399-1407; c)J. Isasi, M.L. Veiga, R. Saez-Puche, A. Jereze, C. Pico, J. Alloys Compd. 1991, 177, 251-257)。最近，中子繞射研究已指示，Li5 La3 M2 O12 (M=Nb、Ta)以空間群Ia3d結晶且Li位於四面體位置及八面體位置且兩類位置中皆存在空位(a)E.J. Cussen, Chem. Commun. 2006, 412-413; b)M.P. O'Callaghan, D.R. Lynham, E.J. Cussen, G.Z. Chen, Chem. Mater. 2006, 18, 4681-4689)。所測Li7 La3 Zr2 O12 之粉末XRD圖案與已知石榴石相Li5 La3 Mb2 O12 之標準圖案非常一致，且證明石榴石結構能夠併有不同氧化態及不同尺寸之陽離子而對稱性無過度變化。測定具有A=12.9682 (6)Å之晶格常數之立方晶胞的繞射圖案。
在18℃下所得之Li7 La3 Zr2 O12 厚片之典型阻抗曲線展示於圖1中。當電極被離子性阻斷時在低頻區域出現的上升指示所檢材料為離子導體(a)V. Thangadurai, R.A. Huggins, W. Weppner, J. Power Sources 2002, 108, 64-69; b)J.T.S. Irvine, D.C. Sinclair, A.R. West, Adv. Mater. 1990, 2, 132-138)。對先前所研究之具有石榴石樣結構的材料已觀測到類似特性。阻抗曲線可分解成體積電阻、晶界電阻及電極電阻。圖1中之連續線呈現(Rb Qb )(Rgb Qgb )(Qel )之等效電路之資料(使用EQUIVALENT程式)。在18℃下所量測之Li7 La3 Zr2 O12 薄片之阻抗曲線以圖1中之插圖展示。在不同溫度下所觀測之Li7 La3 Zr2 O12 厚片(1.02cm厚且直徑0.92cm)及薄片(0.18cm厚且直徑0.98cm)之體積電導率及總電導率由高頻半圓及低頻半圓與軸之交點獲得，且總結於表1中。圖1及表1中所示的資料指示Li7 La3 Zr2 O12 厚片與薄片之類似電特性。與厚片相比，薄片呈現稍微更高的體積電導率及總電導率。此外，有趣的是，對於厚片與薄片皆注意到，晶界電阻對總電阻的貢獻小於50%，且隨溫度 增加而減少(表1)。在較高溫度(對於厚片，75℃以上；且對於薄片，50℃以上)下，與體積電阻貢獻相比，難以精確地測定晶界電阻貢獻；因此展示體積電阻與晶界電阻貢獻之總值用於在所檢查之溫度範圍內測定電導率。與所有其他固態鋰離子導體及所有先前所述之鋰石榴石相比，具有石榴石樣結構之新穎快速結晶鋰離子導體Li7 La3 Zr2 O12 在室溫下的總電導率(在25℃下，3×10-4 S/cm)更佳。
此結果(亦即，總電導率與體積電導率具有相同量值級)為與其他陶瓷鋰離子導體相比，此處所檢查之Li7 La3 Zr2 O12 石榴石結構之尤其有利特性。對於固體電解質在電化學裝置(諸如電池、感測器及電致變色顯示器)中的多種應用，總電導率應儘可能高。此外，體積電導率及總電導率可經由Li7 La3 Zr2 O12 之低溫合成及經由使用適當燒結法進一步緻密化來進一步改良。
以兩個加熱與冷卻循環所得之Li7 La3 Zr2 O12 厚片之體積電導率及總電導率之Arrhenius曲線展示於圖2a中。在兩次循環之間，電導率不存在明顯變化。此意謂，所檢查之石榴石樣結構具有熱穩定性，且在所檢查之溫度範圍(亦即室溫至350℃)內未發生相變。對於Li7 La3 Zr2 O12 薄片亦觀測到類似的Arrhenius特性。在圖2b中，對在各種情況下在首次加熱試驗中獲得之Li7 La3 Zr2 O12 厚片與薄片之資料進行比較。所得針對薄片之體積電導率與總電導率之活化能(在18-50℃下為0.32 eV，且在18-300℃下為0.30 eV)稍微低於針對厚片之體積電導率與總電導率之活化能(在18-70℃ 下為0.34 eV，且在18-300℃下為0.31 eV)。所得薄片之電導率稍微高於厚片之電導率。
除阻抗分析外，電導率之離子性質亦藉由EMF量測法證明，其中使用Li7 La3 Zr2 O12 作為元素鋰與Al之間(LiAl)的固體電解質。將樣本在上側用鋁層覆蓋且置於鋰上，鋰在充有惰性Ar氣體的手套工作箱中已熔融。鋁藉由化學反應與鋰合金化，且亦藉由電量滴定法使鋰自其反向定位之鋰電極進入鋁中而合金化。所得電壓接近理論值。差異可歸於因不可逆過程所致的非均一溫度分布及相應現象。
圖3展示Li7 La3 Zr2 O12 與正考慮結合電池使用之其他已知鋰離子導體之鋰離子電導率的比較。Li7 La3 Zr2 O12 電導率高於Li-β-氧化鋁、薄層Lipon(Li2.9 PO3.3 N0.46 )、Li9 SiAlO8 、Lil+40mol Al2 O3 、LiZr2 (PO4 )3 、Li3.5 Si0.5 P0.5 O4 、Li5 La3 Ta2 O12 及Li6 BaLa2 Ta2 O12 之電導率。可觀測到的比其他含鋰石榴石高的鋰電導率及低活化能可能係由於立方晶格常數增大、鋰離子濃度增大、鋰離子與形成晶格之其他離子之間的化學相互作用減小且部分地由於經改良之緻密化(理論密度之92%)。在相對較低的溫度下，穩定性較小之多晶Li3 N之電導率(在27℃下，6.6×10-4 S/cm)可與Li7 La3 Zr2 O12 之電導率相當。然而，在更高溫度下，Li7 La3 Zr2 O12 呈現更高的總電導率。
Li7 La3 Zr2 O12 之熱穩定性(其為結晶鋰離子導體之基本優勢)可藉由熱解重量量測法(TGA)及差熱分析法(DTA)證明。在空氣氣氛下所量測之TG-DTA資料指示，在加熱期 間與冷卻期間，在20℃至900℃之溫度範圍內，無顯著的質量變化且無可辨識的相變。經數週觀測期發現，含鋯Li7 La3 Zr2 O12 對熔融鋰具有穩定性，且對濕氣及空氣之作用亦具有化學穩定性。
 圖1：
在18℃下、在空氣中對Li7 La3 Zr2 O12 之厚片(1.02cm厚及直徑0.92cm)所量測之AC阻抗曲線。連續線表示等效電路之模擬資料(使用EQUIVALENT程式(B.A. Boukamp, Equivalent Circuit, 4.55版，1997, Faculty of Chemical Technology, University of Twente, 7500 AE Enschede (The Netherlands)，第CT88/265/128/CT89/214/128號報導，1989年5月))，模擬資料包含(Rb Qb )(Rgb Qgb )(Qel )(其中R為電阻且Q為恆相元素，且指數g、gb及el指示顆粒體積、晶界及電極)。在18℃下、在空氣中對Li7 La3 Zr2 O12 薄片(0.18cm厚且直徑0.98cm)所量測的阻抗曲線展示於插圖中。
圖2:
a)以兩個連續加熱與冷卻循環所得之Li7 La3 Zr2 O12 厚片之體積電導率及總電導率(體積與晶界)的Arrhenius曲線。
b)在首次加熱試驗(18-300℃)期間所得之Li7 La3 Zr2 O12 厚片與薄片之Arrhenius曲線之比較。
圖3:
Li7 La3 Zr2 O12 與討論用於電池應用之其他已知鋰離子導體之總電導率(體積＋晶界)之比較。
圖4：
所測Li7 La3 Zr2 O12 之粉末XRD圖案與根據粉末繞射標準聯合委員會(Joint Committee on Powder Diffraction Standards)之已知石榴石相Li5 La3 Nb2 O12 之標準圖案 (JCPDS: 80-0457)。
圖5：
在25℃及50℃下、在空氣中對Li7 La3 Zr2 O12 厚片所量測的AC阻抗曲線。
圖6：
在25℃及50℃下、在空氣中對Li7 La3 Zr2 O12 薄片所量測的AC阻抗曲線。在較高頻率下之另一曲線以插圖形式展示。
圖7：
以兩個連續加熱與冷卻循環所得之Li7 La3 Zr2 O12 薄片之體積電導率與總電導率(體積＋晶界)之Arrhenius曲線。
圖8:
a)Li7 La3 Zr2 O12 片粒與鉬坩堝暴露於熔融鋰之前之像片；b)熔融鋰中之Li7 La3 Zr2 O12 片粒之像片；及c)剛暴露於熔融鋰48小時後之Li7 La3 Zr2 O12 片粒與鉬坩堝之像片。圖c)所示之像片展示片粒顏色保持不變(象牙色)且未形成反應產物。
(無元件符號說明)

Claims (22)

  1. 一種具有石榴石樣晶體結構之固態離子導體用作電極塗層或電極前之保護層的用途。
  2. 一種經塗覆具有石榴石樣晶體結構之固態離子導體的電極。
  3. 一種包含一或多個如請求項2之電極的電池。
  4. 一種具有石榴石樣晶體結構且具有化學計量組成L7+x Ax G3-x Zr2 O12 的固態離子導體，其中：L在各種情況下獨立地為單價陽離子；A在各種情況下獨立地為二價陽離子；G在各種情況下獨立地為三價陽離子；0x3；且O可部分或完全地經二價陰離子或諸如N3- 之三價陰離子置換。
  5. 如請求項4之固態離子導體，其中0x1。
  6. 如請求項4或5之固態離子導體，其中L係選自Li、Na及/或K。
  7. 如請求項6之固態離子導體，其中L=Na。
  8. 如請求項4或5之固態離子導體，其中A為二價鹼土金屬陽離子。
  9. 如請求項4或5之固態離子導體，其中A係選自Ca、Sr及/或Ba。
  10. 如請求項4或5之固態離子導體，其中該化學計量組成為Li7 La3 Zr2 O12 。
  11. 一種製備如請求項4至10中任一項之固態離子導體的方法，其特徵在於使L、A、G及Zr之鹽及/或氧化物彼此反應。
  12. 如請求項11之方法，其特徵在於該反應係藉由前驅物方法進行，例如藉由Pechini方法進行，藉由甘胺酸方法及藉由該等組分之溶解鹽類之沈澱反應進行。
  13. 如請求項11之方法，其特徵在於該反應係以固相反應進行。
  14. 如請求項11或13之方法，其特徵在於L及A係以硝酸鹽、碳酸鹽或氫氧化物之形式使用且與G2 O3 及ZrO2 反應。
  15. 如請求項11或13之方法，其包含以下步驟：a)將原料混合，且使用氧化鋯容器及磨球較佳於2-丙醇中進行球磨；b)在空氣中將獲自a)之混合物在400℃至1000℃下加熱2至10小時；c)球磨，較佳使用氧化鋯容器及磨球於2-丙醇中球磨；d)將該混合物均衡施壓以產生所要形狀；且e)在700℃至1200℃下，將經具有相同組成之粉末覆蓋之獲自步驟d)之產物燒結10至50小時。
  16. 如請求項15之方法，其中該混合物係在步驟b)中在700℃下加熱6小時，且在步驟e)中在900℃下燒結24小時。
  17. 一種如請求項4至10中任一項之固態離子導體在電池、蓄電池、超級電容器、燃料電池、感測器、熱電轉換器及/或諸如視窗、VDU及外牆之電致變色裝置中的用途。
  18. 如請求項1之用途，其中使用一如請求項4至10中任一項之離子導體。
  19. 如請求項2之電極，其中使用一如請求項4至10中任一項之離子導體。
  20. 一種包含一或多個如請求項19之電極的電池。
  21. 如請求項1之用途，其中該固態離子導體係與呈液體、凝膠或固體形式存在之其他電解質併用。
  22. 如請求項1之用途，其中該固態離子導體係與其他液體電解質併用。
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