開發新型態鋰電池以適應日益複雜的使用環境迫在眉睫，因此研究不易燃、高能量密度的固態電解質成為熱門題材。在眾多材料中，石榴石型之鋰鑭鋯氧化合物電解質具備室溫下之高離子導率、對鋰金屬的高穩定性、寬電化學窗口等優點，故在固態電解質領域受到高度關注。然而結晶態的固態電解質仍舊受到鋰枝晶的嚴重影響，並導致電池效能降低等不良表現。眾多文獻已報導鋰枝晶在結晶的固態電解質中主要沿晶界生成，因此具備無晶界特性之非晶態材料在近幾年的研究中開始展露頭角。在本研究中，主要使用射頻磁控濺鍍於室溫下製備不同鋰成分之非晶態鋰鑭鋯氧薄膜來進行分析，並應用於修飾結晶態之固態電解質。此工作首要分析不同鋰成分之非晶態鋰鑭鋯氧薄膜，以交流阻抗和核磁共振光譜交互比較其不同鋰濃度下之傳輸機制，並藉由變溫實驗測量溫度對其傳輸之影響，得出在鋰鑭鋯氧薄膜中增加21.96 wt%比例之鋰含量擁有最佳離子導率(9.32×10-9 S/cm)之非晶態鋰鑭鋯氧薄膜。後續進一步應用非晶薄膜修飾結晶陶瓷電解質的表面，其臨界電流密度從0.15 mA/cm2大幅提升至0.4 mA/cm2。此外，經非晶鋰鑭鋯氧薄膜修飾之結晶電解質，其電子導率相較原先下降至原先的千分之一，對於鋰金屬在電解質內的沉積有優異的抑制效果。透過非晶態鋰鑭鋯氧薄膜對電子之高度阻擋特性，能夠提升電解質使用壽命，不僅能整合於薄膜型全固態電池，同時也能夠應用於修飾其他結晶系界面。

Developers of lithium battery communities are seeking to provide non-flammable and high-energy density solid-state electrolytes (SSEs) in a highly changing environment. Among such candidates, the garnet-type lithium lanthanum zirconium oxide (Li7La3Zr2O12, LLZO) has drawn a lot of attention in the field due to its excellent ionic conductivity at room temperature, high stability to lithium metal, and wide electrochemical window. However, crystalline garnet electrolytes are still severely suffered by lithium dendrites, reducing performance and decreasing battery life. Several works of literature have indicated that lithium dendrites mainly propagate along grain boundaries (GBs) in crystalline SSEs. Herein, the GBs-free characteristic of amorphous materials is proposed to address this issue. In this work, the amorphous thin films of lithium lanthanum zirconium oxide with different lithium portions were prepared by the RF magnetron sputtering at room temperature. Amorphous LLZO thin films were further applied to modify the crystalline SSEs. AC impedance and nuclear magnetic resonance spectroscopy were used to compare the ion transport mechanism under different analyzing scales at various lithium concentrations. Temperature-dependent measurements were also used to calculate the activation energy of transporting barrier. The best ionic conductivity (9.32×10-9 S/cm) of amorphous LLZO was obtained by increasing the lithium portion up to 21.96 wt%. The amorphous thin films were further coated on the surface of the crystalline LLZO-based SSEs to modify the surface and interrupt the lithium propagation paths. The critical current density increased from 0.15 mA/cm2 to 0.4 mA/cm2 after the modification. Furthermore, the electronic conductivity of modified SSEs was also down to one thousandth. Amorphous LLZO thin film demonstrates a high ability against lithium dendrites with GBs-free characteristics, which may integrate with all solid-state thin film batteries, and be applied for modification on crystalline electrolytes.

摘要 i
Abstract ii
致謝 iv
目錄 v
圖目錄 vii
表目錄 x
第一章 介紹 1
1-1前言 1
1-2研究動機 2
第二章 文獻回顧 4
2-1鋰離子電池綜述 4
2-2固態鋰離子電池 7
2-3固態鋰電池種類 9
2-3-1薄膜型固態鋰電池 14
2-4電解質中的鋰枝晶 17
2-4-1液態電解質的鋰枝晶 17
2-4-2固態電解質中的鋰沉積 20
2-5非晶離子導體電解質 25
第三章 實驗 26
3-1材料與製程器材選擇 26
3-2不同鋰含量之非晶態鋰鑭鋯氧薄膜 27
3-3以非晶態鋰鑭鋯氧薄膜修飾鉭摻雜鋰鑭鋯氧陶瓷固態電解質 29
3-4儀器介紹 30
3-4-1低掠角X-Ray繞射儀 30
3-4-2拉曼光譜儀 31
3-4-3核磁共振光譜儀 32
3-4-4飛行時間二次離子質譜儀 34
3-4-5掃描式電子顯微鏡 35
3-4-6臨場觀測型掃描式電子顯微鏡 36
3-4-7電化學阻抗譜 37
第四章 結果與討論 40
4-1非晶態鋰鑭鋯氧薄膜 40
4-1-1 形貌觀測 41
4-1-2 材料相分析 42
4-1-3 成分分析 44
4-1-4 電化學量測結果 48
4-1-5 核磁共振光譜分析 51
4-2以非晶態鋰鑭鋯氧薄膜修飾結晶陶瓷固態電解質 58
4-2-1 結晶陶瓷電解質之充放電臨場觀測 59
4-2-2 比較非晶態薄膜修飾前後之結晶陶瓷電解質 64
4-2-3 比較非晶態薄膜修飾前後之結晶陶瓷電解質 69
4-2-4 比較不同尺度之LLZO結晶電解質阻抗 73
第五章 結論 75
參考文獻 76

1. Gu, Z.-Y., et al., High-rate and long-cycle cathode for sodium-ion batteries: Enhanced electrode stability and kinetics via binder adjustment. ACS Applied Materials & Interfaces, 2020. 12(42): p. 47580-47589.
2. Cheng, X.-B., et al., Toward safe lithium metal anode in rechargeable batteries: a review. Chemical reviews, 2017. 117(15): p. 10403-10473.
3. Tang, L.-b., et al., Boosting cell performance of LiNi0. 8Co0. 1Mn0. 1O2 cathode material via structure design. Journal of Energy Chemistry, 2021. 55: p. 114-123.
4. Armand, M., et al., Building better batteries. nature, 2008. 451(7179): p. 652-657.
5. Li, W., et al., A PEO-based gel polymer electrolyte for lithium ion batteries. RSC advances, 2017. 7(38): p. 23494-23501.
6. Mukhopadhyay, A., et al., Li metal battery, heal thyself. Science, 2018. 359(6383): p. 1463-1463.
7. Hannan, M., et al., Review of energy storage systems for electric vehicle applications: Issues and challenges. Renewable and Sustainable Energy Reviews, 2017. 69: p. 771-789.
8. Gao, T., et al., Mechanism and effect of thermal degradation on electrolyte ionic diffusivity in Li-ion batteries: A molecular dynamics study. Electrochimica Acta, 2019. 323: p. 134791.
9. Campion, C.L., et al., Thermal decomposition of LiPF6-based electrolytes for lithium-ion batteries. Journal of The Electrochemical Society, 2005. 152(12): p. A2327.
10. Li, W., et al., Additives for stabilizing LiPF6-based electrolytes against thermal decomposition. Journal of the Electrochemical Society, 2005. 152(7): p. A1361.
11. Kraft, V., et al., Two-dimensional ion chromatography for the separation of ionic organophosphates generated in thermally decomposed lithium hexafluorophosphate-based lithium ion battery electrolytes. Journal of Chromatography A, 2015. 1409: p. 201-209.
12. Kerner, M., et al., Thermal stability and decomposition of lithium bis (fluorosulfonyl) imide (LiFSI) salts. Rsc Advances, 2016. 6(28): p. 23327-23334.
13. Wilken, S., et al., Infrared spectroscopy of instantaneous decomposition products of LiPF6-based lithium battery electrolytes. Solid State Ionics, 2012. 225: p. 608-610.
14. Ravdel, B., et al., Thermal stability of lithium-ion battery electrolytes. Journal of Power Sources, 2003. 119: p. 805-810.
15. Handel, P., et al., Thermal aging of electrolytes used in lithium-ion batteries–An investigation of the impact of protic impurities and different housing materials. Journal of Power Sources, 2014. 267: p. 255-259.
16. Lux, S., et al., The mechanism of HF formation in LiPF6 based organic carbonate electrolytes. Electrochemistry Communications, 2012. 14(1): p. 47-50.
17. Vetter, J., et al., Ageing mechanisms in lithium-ion batteries. Journal of power sources, 2005. 147(1-2): p. 269-281.
18. Lu, D., et al., Failure mechanism for fast‐charged lithium metal batteries with liquid electrolytes. Advanced Energy Materials, 2015. 5(3): p. 1400993.
19. Bieker, G., et al., Electrochemical in situ investigations of SEI and dendrite formation on the lithium metal anode. Physical Chemistry Chemical Physics, 2015. 17(14): p. 8670-8679.
20. Holmberg, K., et al., Influence of tribology on global energy consumption, costs and emissions. Friction, 2017. 5(3): p. 263-284.
21. Armand, M., Intercalation electrodes, in Materials for advanced batteries. 1980, Springer. p. 145-161.
22. Bruce, P.G., et al., The A‐C conductivity of polycrystalline LISICON, Li2+ 2x Zn1− x GeO4, and a model for intergranular constriction resistances. Journal of The Electrochemical Society, 1983. 130(3): p. 662.
23. Nolan, A.M., et al., Computation-accelerated design of materials and interfaces for all-solid-state lithium-ion batteries. Joule, 2018. 2(10): p. 2016-2046.
24. Manthiram, A., et al., Lithium battery chemistries enabled by solid-state electrolytes. Nature Reviews Materials, 2017. 2(4): p. 1-16.
25. Hess, S., et al., Flammability of Li-ion battery electrolytes: flash point and self-extinguishing time measurements. Journal of The Electrochemical Society, 2015. 162(2): p. A3084.
26. Li, Q., et al., Progress in electrolytes for rechargeable Li-based batteries and beyond. Green Energy & Environment, 2016. 1(1): p. 18-42.
27. Di Lecce, D., et al., Rechargeable lithium battery using non-flammable electrolyte based on tetraethylene glycol dimethyl ether and olivine cathodes. Journal of Power Sources, 2016. 334: p. 146-153.
28. Wang, Q., et al., Progress of enhancing the safety of lithium ion battery from the electrolyte aspect. Nano Energy, 2019. 55: p. 93-114.
29. Jiang, W., et al., A high temperature operating nanofibrous polyimide separator in Li-ion battery. Solid State Ionics, 2013. 232: p. 44-48.
30. Lee, H., et al., Energy Environ Sci 7: 3857 https://doi. org/10.1039. 2014, C4EE01432D.
31. Li, C., et al., An advance review of solid-state battery: Challenges, progress and prospects. Sustainable Materials and Technologies, 2021. 29: p. e00297.
32. Gambe, Y., et al., Development of bipolar all-solid-state lithium battery based on quasi-solid-state electrolyte containing tetraglyme-LiTFSA equimolar complex. Scientific reports, 2015. 5(1): p. 1-4.
33. Liang, J., et al., Recent progress on solid-state hybrid electrolytes for solid-state lithium batteries. Energy Storage Materials, 2019. 21: p. 308-334.
34. Xia, Y., et al., Thermal and electrochemical stability of cathode materials in solid polymer electrolyte. Journal of Power Sources, 2001. 92(1-2): p. 234-243.
35. Hu, Q., et al., Graft copolymer-based lithium-ion battery for high-temperature operation. Journal of Power Sources, 2011. 196(13): p. 5604-5610.
36. Novák, P., et al., A high-temperature lithium copper oxide cell with a solid polymer electrolyte. Journal of power sources, 1991. 35(3): p. 235-247.
37. Harry, K.J., et al., Detection of subsurface structures underneath dendrites formed on cycled lithium metal electrodes. Nature materials, 2014. 13(1): p. 69-73.
38. Yang, C., et al., Protected lithium‐metal anodes in batteries: from liquid to solid. Advanced materials, 2017. 29(36): p. 1701169.
39. Kumazaki, S., et al., High lithium ion conductive Li7La3Zr2O12 by inclusion of both Al and Si. Electrochemistry communications, 2011. 13(5): p. 509-512.
40. Geiger, C.A., et al., Crystal chemistry and stability of “Li7La3Zr2O12” garnet: a fast lithium-ion conductor. Inorganic chemistry, 2011. 50(3): p. 1089-1097.
41. Murugan, R., et al., Fast lithium ion conduction in garnet‐type Li7La3Zr2O12. Angewandte Chemie International Edition, 2007. 46(41): p. 7778-7781.
42. Im, C., et al., Al-incorporation into Li7La3Zr2O12 solid electrolyte keeping stabilized cubic phase for all-solid-state Li batteries. Journal of energy chemistry, 2018. 27(5): p. 1501-1508.
43. Matsui, M., et al., Phase stability of a garnet-type lithium ion conductor Li 7 La 3 Zr 2 O 12. Dalton Transactions, 2014. 43(3): p. 1019-1024.
44. Zhou, Y.-N., et al., Nanostructured thin film electrodes for lithium storage and all-solid-state thin-film lithium batteries. Journal of Power Sources, 2013. 234: p. 310-332.
45. Zheng, N., et al., Synthetic design of crystalline inorganic chalcogenides exhibiting fast-ion conductivity. Nature, 2003. 426(6965): p. 428-432.
46. Mizuno, F., et al., New lithium-ion conducting crystal obtained by crystallization of the Li2S–P2S5 glasses. Electrochemical and Solid-State Letters, 2005. 8(11): p. A603.
47. Wu, J., et al., Lithium/sulfide all‐solid‐state batteries using sulfide electrolytes. Advanced Materials, 2021. 33(6): p. 2000751.
48. Muramatsu, H., et al., Structural change of Li2S–P2S5 sulfide solid electrolytes in the atmosphere. Solid State Ionics, 2011. 182(1): p. 116-119.
49. Ohtomo, T., et al., All-solid-state lithium secondary batteries using the 75Li2S· 25P2S5 glass and the 70Li2S· 30P2S5 glass–ceramic as solid electrolytes. Journal of Power Sources, 2013. 233: p. 231-235.
50. Meesala, Y., et al., Recent advancements in Li-ion conductors for all-solid-state Li-ion batteries. ACS Energy Letters, 2017. 2(12): p. 2734-2751.
51. Hatzell, K.B., et al., Challenges in lithium metal anodes for solid-state batteries. ACS Energy Letters, 2020. 5(3): p. 922-934.
52. Wang, C., et al., Garnet-type solid-state electrolytes: materials, interfaces, and batteries. Chemical reviews, 2020. 120(10): p. 4257-4300.
53. Thangadurai, V., et al., Novel fast lithium ion conduction in garnet‐type Li5La3M2O12 (M= Nb, Ta). Journal of the American Ceramic Society, 2003. 86(3): p. 437-440.
54. Thangadurai, V., et al., Garnet-type solid-state fast Li ion conductors for Li batteries: critical review. Chemical Society Reviews, 2014. 43(13): p. 4714-4727.
55. Bates, J., et al., Electrical properties of amorphous lithium electrolyte thin films. Solid state ionics, 1992. 53: p. 647-654.
56. Qin, S., et al., Extremely dense microstructure and enhanced ionic conductivity in hot-isostatic pressing treated cubic garnet-type solid electrolyte of Ga2O3-doped Li7La3Zr2O12. Functional Materials Letters, 2018. 11(02): p. 1850029.
57. Kamaya, N., et al., A lithium superionic conductor. Nature materials, 2011. 10(9): p. 682-686.
58. Zhu, Y., et al., Origin of outstanding stability in the lithium solid electrolyte materials: insights from thermodynamic analyses based on first-principles calculations. ACS applied materials & interfaces, 2015. 7(42): p. 23685-23693.
59. Minami, T., et al., Recent progress of glass and glass-ceramics as solid electrolytes for lithium secondary batteries. Solid State Ionics, 2006. 177(26-32): p. 2715-2720.
60. Shimonishi, Y., et al., Synthesis of garnet-type Li7− xLa3Zr2O12− 1/2x and its stability in aqueous solutions. Solid State Ionics, 2011. 183(1): p. 48-53.
61. Rangasamy, E., et al., The role of Al and Li concentration on the formation of cubic garnet solid electrolyte of nominal composition Li7La3Zr2O12. Solid State Ionics, 2012. 206: p. 28-32.
62. Li, Y., et al., High lithium ion conduction in garnet-type Li6La3ZrTaO12. Electrochemistry Communications, 2011. 13(12): p. 1289-1292.
63. Awaka, J., et al., Synthesis and structure analysis of tetragonal Li7La3Zr2O12 with the garnet-related type structure. Journal of solid state chemistry, 2009. 182(8): p. 2046-2052.
64. Cussen, E.J., Structure and ionic conductivity in lithium garnets. Journal of Materials Chemistry, 2010. 20(25): p. 5167-5173.
65. Narayanan, S., et al., Enhancing Li ion conductivity of garnet-type Li5La3Nb2O12 by Y-and Li-codoping: synthesis, structure, chemical stability, and transport properties. The Journal of Physical Chemistry C, 2012. 116(38): p. 20154-20162.
66. Duvel, A., et al., Mechanosynthesis of solid electrolytes: preparation, characterization, and Li ion transport properties of garnet-type Al-doped Li7La3Zr2O12 crystallizing with cubic symmetry. The Journal of Physical Chemistry C, 2012. 116(29): p. 15192-15202.
67. Liu, Q., et al., Challenges and perspectives of garnet solid electrolytes for all solid-state lithium batteries. Journal of Power Sources, 2018. 389: p. 120-134.
68. Awaka, J., et al., Crystal structure of fast lithium-ion-conducting cubic Li7La3Zr2O12. Chemistry letters, 2011. 40(1): p. 60-62.
69. Bernstein, N., et al., Origin of the structural phase transition in Li 7 La 3 Zr 2 O 12. Physical review letters, 2012. 109(20): p. 205702.
70. Raju, M.M., et al., Crystal structure and preparation of Li7La3Zr2O12 (LLZO) solid-state electrolyte and doping impacts on the conductivity: An overview. Electrochem, 2021. 2(3): p. 390-414.
71. Han, J., et al., Experimental visualization of lithium conduction pathways in garnet-type Li 7 La 3 Zr 2 O 12. Chemical Communications, 2012. 48(79): p. 9840-9842.
72. Bates, J., et al., Thin-film lithium and lithium-ion batteries. Solid state ionics, 2000. 135(1-4): p. 33-45.
73. Neudecker, B., et al., Lithium silicon tin oxynitride (LiySiTON): high-performance anode in thin-film lithium-ion batteries for microelectronics. Journal of power sources, 1999. 81: p. 27-32.
74. Baba, M., et al., Fabrication and Electrochemical Characteristics of All‐Solid‐State Lithium‐Ion Batteries Using V 2 O 5 Thin Films for Both Electrodes. Electrochemical and solid-state letters, 1999. 2(7): p. 320.
75. Neudecker, B., et al., “Lithium‐free” thin‐film battery with in situ plated Li anode. Journal of the Electrochemical Society, 2000. 147(2): p. 517.
76. Kanehori, K., et al., Thin film solid electrolyte and its application to secondary lithium cell. Solid State Ionics, 1983. 9: p. 1445-1448.
77. Lobe, S., et al., Radio frequency magnetron sputtering of Li7La3Zr2O12 thin films for solid-state batteries. Journal of power sources, 2016. 307: p. 684-689.
78. Indrizzi, L., et al., Pulsed Laser Deposition as a tool for the development of all solid‐state microbatteries. Helvetica Chimica Acta, 2021. 104(2): p. e2000203.
79. Futscher, M.H., et al., Influence of amorphous carbon interlayers on nucleation and early growth of lithium metal at the current collector-solid electrolyte interface. Journal of Materials Chemistry A, 2022. 10(29): p. 15535-15542.
80. Sastre, J., et al., Blocking lithium dendrite growth in solid-state batteries with an ultrathin amorphous Li-La-Zr-O solid electrolyte. Communications Materials, 2021. 2(1): p. 1-10.
81. Takada, K., Progress in solid electrolytes toward realizing solid-state lithium batteries. Journal of Power Sources, 2018. 394: p. 74-85.
82. Lee, S.H., et al., All‐solid‐state rocking chair lithium battery on a flexible al substrate. Electrochemical and solid-state letters, 1999. 2(9): p. 425.
83. Koo, M., et al., Bendable inorganic thin-film battery for fully flexible electronic systems. Nano letters, 2012. 12(9): p. 4810-4816.
84. Kato, Y., et al., High-power all-solid-state batteries using sulfide superionic conductors. Nature Energy, 2016. 1(4): p. 1-7.
85. Liu, B., et al., Advancing lithium metal batteries. Joule, 2018. 2(5): p. 833-845.
86. Shen, X., et al., Beyond lithium ion batteries: Higher energy density battery systems based on lithium metal anodes. Energy Storage Materials, 2018. 12: p. 161-175.
87. Tan, S.J., et al., Nitriding‐interface‐regulated lithium plating enables flame‐retardant electrolytes for high‐voltage lithium metal batteries. Angewandte Chemie, 2019. 131(23): p. 7884-7889.
88. Li, L., et al., Suppression of dendritic lithium growth in lithium metal-based batteries. Chemical communications, 2018. 54(50): p. 6648-6661.
89. Sacci, R.L., et al., Direct visualization of initial SEI morphology and growth kinetics during lithium deposition by in situ electrochemical transmission electron microscopy. Chemical Communications, 2014. 50(17): p. 2104-2107.
90. Stark, J.K., et al., Nucleation of electrodeposited lithium metal: dendritic growth and the effect of co-deposited sodium. Journal of The Electrochemical Society, 2013. 160(9): p. D337.
91. Feng Shanshan, L.X., et al., Nucleation, growth and inhibition of lithium dendrites. CIESC Journal, 2022. 73(1): p. 97-109.
92. Chen, X.R., et al., A diffusion‐‐reaction competition mechanism to tailor lithium deposition for lithium‐metal batteries. Angewandte Chemie International Edition, 2020. 59(20): p. 7743-7747.
93. Zou, P., et al., Polymorph evolution mechanisms and regulation strategies of lithium metal anode under multiphysical fields. Chemical Reviews, 2021. 121(10): p. 5986-6056.
94. Chazalviel, J.-N., Electrochemical aspects of the generation of ramified metallic electrodeposits. Physical review A, 1990. 42(12): p. 7355.
95. Fleury, V., et al., The role of the anions in the growth speed of fractal electrodeposits. Journal of electroanalytical chemistry and interfacial electrochemistry, 1990. 290(1-2): p. 249-255.
96. Kushima, A., et al., Liquid cell transmission electron microscopy observation of lithium metal growth and dissolution: Root growth, dead lithium and lithium flotsams. Nano Energy, 2017. 32: p. 271-279.
97. Jana, A., et al., Lithium dendrite growth mechanisms in liquid electrolytes. Nano Energy, 2017. 41: p. 552-565.
98. Aryanfar, A., et al., Thermal relaxation of lithium dendrites. Physical Chemistry Chemical Physics, 2015. 17(12): p. 8000-8005.
99. Monroe, C., et al., The impact of elastic deformation on deposition kinetics at lithium/polymer interfaces. Journal of The Electrochemical Society, 2005. 152(2): p. A396.
100. Monroe, C., et al., The effect of interfacial deformation on electrodeposition kinetics. Journal of The Electrochemical Society, 2004. 151(6): p. A880.
101. Sudo, R., et al., Interface behavior between garnet-type lithium-conducting solid electrolyte and lithium metal. Solid State Ionics, 2014. 262: p. 151-154.
102. Zeng, X.-X., et al., Reshaping lithium plating/stripping behavior via bifunctional polymer electrolyte for room-temperature solid Li metal batteries. Journal of the American Chemical Society, 2016. 138(49): p. 15825-15828.
103. Wang, M., et al., Correlating the interface resistance and surface adhesion of the Li metal-solid electrolyte interface. Journal of Power Sources, 2018. 377: p. 7-11.
104. Han, F., et al., High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes. Nature Energy, 2019. 4(3): p. 187-196.
105. Porz, L., et al., Mechanism of lithium metal penetration through inorganic solid electrolytes. Advanced Energy Materials, 2017. 7(20): p. 1701003.
106. Duan, H., et al., Stability of garnet-type Li ion conductors: An overview. Solid State Ionics, 2018. 318: p. 45-53.
107. Yang, C., et al., Continuous plating/stripping behavior of solid-state lithium metal anode in a 3D ion-conductive framework. Proceedings of the National Academy of Sciences, 2018. 115(15): p. 3770-3775.
108. Wu, B., et al., The role of the solid electrolyte interphase layer in preventing Li dendrite growth in solid-state batteries. Energy & Environmental Science, 2018. 11(7): p. 1803-1810.
109. Fu, K., et al., Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface. Science Advances, 2017. 3(4): p. e1601659.
110. Sharafi, A., et al., Surface chemistry mechanism of ultra-low interfacial resistance in the solid-state electrolyte Li7La3Zr2O12. Chemistry of Materials, 2017. 29(18): p. 7961-7968.
111. Tsai, C.-L., et al., Li7La3Zr2O12 interface modification for Li dendrite prevention. ACS applied materials & interfaces, 2016. 8(16): p. 10617-10626.
112. Ren, Y., et al., Direct observation of lithium dendrites inside garnet-type lithium-ion solid electrolyte. Electrochemistry Communications, 2015. 57: p. 27-30.
113. Cheng, E.J., et al., Intergranular Li metal propagation through polycrystalline Li6. 25Al0. 25La3Zr2O12 ceramic electrolyte. Electrochimica Acta, 2017. 223: p. 85-91.
114. Suzuki, Y., et al., Transparent cubic garnet-type solid electrolyte of Al2O3-doped Li7La3Zr2O12. Solid State Ionics, 2015. 278: p. 172-176.
115. Liu, H., et al., Controlling dendrite growth in solid-state electrolytes. ACS Energy Letters, 2020. 5(3): p. 833-843.
116. Ansell, R., The chemical and electrochemical stability of beta-alumina. Journal of materials science, 1986. 21(2): p. 365-379.
117. Yu, S., et al., Grain boundary softening: a potential mechanism for lithium metal penetration through stiff solid electrolytes. ACS applied materials & interfaces, 2018. 10(44): p. 38151-38158.
118. Bachman, J.C., et al., Inorganic solid-state electrolytes for lithium batteries: mechanisms and properties governing ion conduction. Chemical reviews, 2016. 116(1): p. 140-162.
119. Liu, X., et al., Local electronic structure variation resulting in Li ‘filament’formation within solid electrolytes. Nature Materials, 2021. 20(11): p. 1485-1490.
120. Ni, J.E., et al., Room temperature elastic moduli and Vickers hardness of hot-pressed LLZO cubic garnet. Journal of Materials Science, 2012. 47(23): p. 7978-7985.
121. Ma, C., et al., Interfacial stability of Li metal–solid electrolyte elucidated via in situ electron microscopy. Nano letters, 2016. 16(11): p. 7030-7036.
122. Samson, A.J., et al., A bird's-eye view of Li-stuffed garnet-type Li 7 La 3 Zr 2 O 12 ceramic electrolytes for advanced all-solid-state Li batteries. Energy & Environmental Science, 2019. 12(10): p. 2957-2975.
123. Janek, J., et al., A solid future for battery development. Nature Energy, 2016. 1(9): p. 1-4.
124. Krauskopf, T., et al., Physicochemical concepts of the lithium metal anode in solid-state batteries. Chemical reviews, 2020. 120(15): p. 7745-7794.
125. Huang, W., et al., Can we find solution to eliminate Li penetration through solid garnet electrolytes? Materials Today Nano, 2020. 10: p. 100075.
126. Kim, J.-S., et al., Origin of intergranular Li metal propagation in garnet-based solid electrolyte by direct electronic structure analysis and performance improvement by bandgap engineering. Journal of Materials Chemistry A, 2020. 8(33): p. 16892-16901.
127. Kalita, D., et al., Ionic conductivity properties of amorphous Li–La–Zr–O solid electrolyte for thin film batteries. Solid State Ionics, 2012. 229: p. 14-19.
128. Al-Taay, H., et al., Preparation and characterization of silicon nanowires catalyzed by aluminum. Physica E: Low-dimensional Systems and Nanostructures, 2013. 48: p. 21-28.
129. Gittleson, F.S., et al., Raman spectroscopy in lithium–oxygen battery systems. ChemElectroChem, 2015. 2(10): p. 1446-1457.
130. Pfenninger, R., et al., A low ride on processing temperature for fast lithium conduction in garnet solid-state battery films. Nature Energy, 2019. 4(6): p. 475-483.
131. Wang, Z., et al., Composition dependence of lithium diffusion in lithium silicide: a density functional theory study. ChemElectroChem, 2015. 2(9): p. 1292-1297.
132. Kolding, J., Conductivity and Defects in Al-doped Li7La3Zr2O12-A solid-state Li-ion conductor. 2019.
133. Koch, B., et al., Lithium ionic jump motion in the fast solid ion conductor Li5La3Nb2O12. Solid State Nuclear Magnetic Resonance, 2008. 34(1-2): p. 37-43.
134. Meyer, B.M., et al., High field multinuclear NMR investigation of the SEI layer in lithium rechargeable batteries. Electrochemical and solid-state letters, 2005. 8(3): p. A145.
135. Hayamizu, K., et al., Lithium ion micrometer diffusion in a garnet-type cubic Li7La3Zr2O12 (LLZO) studied using 7Li NMR spectroscopy. The Journal of Chemical Physics, 2017. 146(2): p. 024701.
136. Dubouis, N., et al., The role of the hydrogen evolution reaction in the solid–electrolyte interphase formation mechanism for “Water-in-Salt” electrolytes. Energy & Environmental Science, 2018. 11(12): p. 3491-3499.
137. Liu, T., et al., Understanding LiOH Chemistry in a Ruthenium‐Catalyzed Li–O2 Battery. Angewandte Chemie, 2017. 129(50): p. 16273-16278.
138. Bernuy-Lopez, C., et al., Atmosphere controlled processing of Ga-substituted garnets for high Li-ion conductivity ceramics. Chemistry of materials, 2014. 26(12): p. 3610-3617.
139. Larraz, G., et al., NMR study of Li distribution in Li 7− x H x La 3 Zr 2 O 12 garnets. Journal of Materials Chemistry A, 2015. 3(10): p. 5683-5691.
140. van Wüllen, L., et al., The mechanism of Li-ion transport in the garnet Li 5 La 3 Nb 2 O 12. Physical Chemistry Chemical Physics, 2007. 9(25): p. 3298-3303.
141. Cussen, E.J., The structure of lithium garnets: cation disorder and clustering in a new family of fast Li+ conductors. Chemical Communications, 2006(4): p. 412-413.
142. Dumon, A., et al., High Li ion conductivity in strontium doped Li7La3Zr2O12 garnet. Solid State Ionics, 2013. 243: p. 36-41.
143. Kokal, I., et al., Sol–gel synthesis and lithium ion conductivity of Li7La3Zr2O12 with garnet-related type structure. Solid State Ionics, 2011. 185(1): p. 42-46.
144. Chen, R.-J., et al., Sol–gel derived Li–La–Zr–O thin films as solid electrolytes for lithium-ion batteries. Journal of Materials Chemistry A, 2014. 2(33): p. 13277-13282.
145. Shao, C., et al., Structure and ionic conductivity of cubic Li7La3Zr2O12 solid electrolyte prepared by chemical co-precipitation method. Solid State Ionics, 2016. 287: p. 13-16.