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| ???org.dspace.app.webui.jsptag.ItemTag.dcfield??? | Value | Language |
|---|---|---|
| dc.contributor.advisor | 郭錦龍 | zh_TW |
| dc.contributor.advisor | Chin-Lung Kuo | en |
| dc.contributor.author | 劉修志 | zh_TW |
| dc.contributor.author | Hsiu-Chih Liu | en |
| dc.date.accessioned | 2025-02-21T16:18:29Z | - |
| dc.date.available | 2025-02-22 | - |
| dc.date.copyright | 2025-02-21 | - |
| dc.date.issued | 2024 | - |
| dc.date.submitted | 2024-12-23 | - |
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/96733 | - |
| dc.description.abstract | 固態電解質(SSEs)對於開發更安全、更穩定的鋰離子電池至關重要。本研究運用DFT模擬、AIMD和NEB，研究了石榴石型固態電解質Li7La3Zr2O12 (LLZO)在不同摻雜條件下的結構穩定性和鋰離子擴散機制。我們通過詳細分析四面體位置(T-site)占據率、空缺分布、平均平方位移和能障，來探討了鎵(Ga)和鋁(Al)摻雜對相變和離子電導率的影響。藉由能量分析，我們發現在0K下的立方相和四方晶相存在著顯著的四面體位置占據率，立方相具有較高的四面體位置占據率而後者的四面體位置占據率則較低，利用參雜，可以藉由改變參雜附近的原子排列來達到更高的四面體位置占據率，並使得立方相在參雜到一定濃度後具有較穩定的能量，所以參雜對立方相的LLZO具有穩定效果，值得注意的一點是，鎵(Ga)和鋁(Al)其實對於穩定立方相LLZO有類似的效果。
Ia-3d(230)到I-43d(220)最大的差異在於鋰所在之四面體位置有是否可以分辨，如果可以分辨成12a和12b，說明此系統為220空間群，若無法分辨為12a和12b，則統一利用24d進行描述，是為230空間群，在進行AIMD時，我們發現參雜系統相較於純系統具有主導的四面體位置(12b)，而純系統的四面體位置會隨著時間的推移出現不同的主導四面體位置，說明純系統的四面體其實並不可分辨，而參雜系統中，隨著參雜濃度的提升，其主導的四面體位置佔據率越高，所以可以知道隨著較高的參雜濃度，LLZO系統也是越趨近於220空間群的。 我們的研究揭示了摻雜濃度、溫度和離子電導率之間的複雜關係。在低溫條件下(1000K以下)，少量摻雜通過維持空間群I-43d(220)的特性來提高電導率。較高的摻雜濃度具有更明顯空間群I-43d(220)的特徵，但是因為活性空缺減少和阻塞效應增加反而會降低電導率。在純LLZO系統中，會出現有序區和無序區，前者有明顯的主導四面體位置而後者沒有，而在無序區中會出現穩定的T-site配對來困住鋰空缺，致使純系統在低溫下表現出較低的電導率，但在高溫下(1000K以上)因為沒有摻雜物引起的阻塞效應而表現出相對優異的性能。藉由觀察AIMD的擴散行為，我們發現了在220空間群中有兩個主要的擴散行為，分別為(1.)12b位置到八面體位置以及(2.)八面體位置到八面體位置兩種，對於擴散行為來說，後者為速率決定步驟，而我們也發現鎵(Ga)系統具有較小的能障，而這和AIMD的結果具有一致性。這些發現為優化下一代電池應用中的LLZO基固態電解質提供了新的見解。 | zh_TW |
| dc.description.abstract | Solid-state electrolytes (SSEs) are crucial for developing safer and more stable lithium-ion batteries. This study employs DFT simulations on static calculation, AIMD, and NEB to investigate the structural stability and Li-ion diffusion mechanisms in garnet-type Li7La3Zr2O12 (LLZO) under different doping conditions. We examine how Ga and Al doping affects the phase transitions and ionic conductivity through detailed analysis of tetrahedral site (T-site) occupancy, vacancy distribution, mean square displacement, and energy barriers.
Through energy analysis, we find that at 0K, both cubic and tetragonal phases exhibit distinct tetrahedral site occupancies, with the cubic phase showing higher occupancy than the tetragonal phase. Through doping, we can achieve higher tetrahedral site occupancy by modifying the atomic arrangement near the dopants, leading to enhanced stability of the cubic phase at sufficient doping concentrations. Notably, both Ga and Al demonstrate similar stabilizing effects on cubic LLZO. The key difference between Ia-3d(230) and I-43d(220) lies in the distinguishability of Li tetrahedral sites. If the sites can be differentiated into 12a and 12b, the system belongs to space group 220; if indistinguishable, they are described uniformly as 24d sites in space group 230. Our AIMD simulations reveal that doped systems exhibit a dominant tetrahedral site (12b), while in pure systems, the dominant tetrahedral site changes over time, indicating indistinguishable tetrahedral sites. As doping concentration increases, the occupancy of the dominant tetrahedral site increases, suggesting the system increasingly adopts space group 220 characteristics. Our research reveals complex relationships between doping concentration, temperature, and ionic conductivity. At low temperatures (below 1000K), low-level doping enhances conductivity by maintaining space group I-43d(220) characteristics. Higher doping concentrations also maintain space group I-43d(220) but decrease conductivity due to reduced active vacancies and increased blocking effects. Pure LLZO exhibits ordered and disordered regions, with the former showing dominant tetrahedral sites while the latter lacks them. Stable T-site pairs in disordered regions trap Li vacancies, resulting in lower conductivity at low temperatures, but superior performance at high temperatures (above 1000K) due to the absence of dopant-induced blocking effects. Through AIMD diffusion behavior observations, we identify two primary diffusion mechanisms in space group 220: (1) 12b site-to-O-site migration and (2) O-site-to-O-site exchange. The latter serves as the rate-determining step, with Ga-doped systems showing lower energy barriers, consistent with AIMD results. These findings provide new insights for optimizing LLZO-based solid electrolytes in next-generation battery applications. | en |
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| dc.description.provenance | Made available in DSpace on 2025-02-21T16:18:29Z (GMT). No. of bitstreams: 0 | en |
| dc.description.tableofcontents | 致謝 iii
摘要 v Abstract vii Contents ix List of Figures xiii List of Tables xvii Chapter 1. Introduction and Paper review p1 1.1 Li-ion Battery p1 1.2 Solid-state Electrolyte p3 1.3 Garnet-like SSEs p4 1.3.1 Brief introduction for Garnet-like SSEs p4 1.3.2 LLZO p6 1.4 Phase issue and Site occupancy issue for LLZO p9 1.4.1 Site occupancy issue p9 1.4.2 Phase transition p11 1.4.2.1 Tetragonal to Cubic Phase Transition p11 1.4.2.2 Ia¯3d(230) to I¯43d(220) Transition within the Cubic Phase p13 1.4.2.3 Relationship between the Two Transitions p13 1.5 Role of Li vacancies in the LLZO p16 1.6 Activation Energy p18 Chapter 2. Methodology p21 2.1 First-principles calculation p21 2.2 Born-Oppenheimer Approximation p21 2.3 Density Functional Theory, DFT p23 2.3.1 Thomas-Fermi model, TF model p23 2.3.2 Hohenberg-Khon theorem p24 2.3.3 Khon-Sham equation p24 2.3.4 Exchange-Correlation function p27 2.3.5 Pseudopotential p27 2.3.6 DDEC6 p29 2.4 NEBM p30 2.5 Molecular dynamics, MD p32 2.5.1 Verlet algorithm p32 2.5.2 Nosé-Hoover thermostat p33 Chapter 3. First-principles calculations of the structure stability and the phase transitions for pure system and Ga/Al-doped systems p35 3.1 Introduction p35 3.2 Computational Details p36 3.3 Structure construction p38 3.4 The definition of 230 and 220 space group p40 3.5 Pure system p43 3.5.1 The type1 method: T-site occupancy more than 12 p45 3.5.2 The type1 method: T-site occupancy less than or equal to 12 p47 3.5.2.1 Three-fold point group p47 3.5.2.2 Inversion four-fold point group p49 3.5.3 The type2 method p52 3.5.4 Convex energy hull in different T-site occupancy p54 3.5.5 The mechanism for phase transition from T-phase to C-phase p58 3.6 Doping system p62 3.6.1 Pre-test p63 3.6.1.1 The site for Dopants p63 3.6.1.2 The local environment of Dopant p64 3.6.1.3 Conclusion form Pre-test p64 3.6.2 Construction of single dopant system p66 3.6.3 Construction of double dopant system p68 3.6.4 Construction of triple dopant system p70 3.7 Summary p73 Chapter 4. The migration behavior of Li ions/vacancies in LLZO p75 4.1 AIMD p75 4.1.1 Convergence test p77 4.1.2 Thermal expansion p78 4.1.3 Vacancy effect p81 4.1.4 MD in different dopant system p83 4.1.4.1 Introduction p83 4.1.4.2 Comparison of the structures between MD and type1 method p83 4.1.4.3 Kinetic Analysis p84 4.1.5 Occupancy in MD simulation p87 4.1.5.1 Introduction p87 4.1.5.2 Occupancy at 700K p87 4.1.5.3 Occupancy at 1000K p91 4.1.5.4 Conclusion p94 4.2 NEB p95 4.2.1 Observation for the migration behavior in the LLZO system p95 4.2.1.1 pure system p98 4.2.1.2 dopant system p100 4.2.2 2 basic migration behavior p102 4.2.3 NEB samples for space group 230 p108 4.2.3.1 Appearance of 12a sites p108 4.2.3.2 Annihilation of 12a sites p110 4.3 Summary p113 Chapter 5. Conclusion p115 References p117 | - |
| dc.language.iso | en | - |
| dc.subject | 固態電解質 | zh_TW |
| dc.subject | 密度泛涵理論 | zh_TW |
| dc.subject | 擴散 | zh_TW |
| dc.subject | 相變 | zh_TW |
| dc.subject | 鋰鑭鋯氧化合物 | zh_TW |
| dc.subject | SSEs | en |
| dc.subject | DFT | en |
| dc.subject | diffusion | en |
| dc.subject | phase transitions | en |
| dc.subject | LLZO | en |
| dc.title | 利用第一原理研究鎵/鋁摻雜對鋰鑭鋯氧化合物(LLZO)結構穩定性以及鋰離子擴散機制的影響 | zh_TW |
| dc.title | First-principles study of Ga/Al doping effects on structure stability and lithium diffusion mechanisms in LLZO | en |
| dc.type | Thesis | - |
| dc.date.schoolyear | 113-1 | - |
| dc.description.degree | 碩士 | - |
| dc.contributor.oralexamcommittee | 李祐慈;李明憲;許文東;蔡秉鈞 | zh_TW |
| dc.contributor.oralexamcommittee | Yu-Tzu Li;Ming-Hsien Lee;Wen-Dung Hsu;Ping-Chun Tsai | en |
| dc.subject.keyword | 固態電解質,鋰鑭鋯氧化合物,相變,擴散,密度泛涵理論, | zh_TW |
| dc.subject.keyword | SSEs,LLZO,phase transitions,diffusion,DFT, | en |
| dc.relation.page | 122 | - |
| dc.identifier.doi | 10.6342/NTU202404761 | - |
| dc.rights.note | 未授權 | - |
| dc.date.accepted | 2024-12-23 | - |
| dc.contributor.author-college | 工學院 | - |
| dc.contributor.author-dept | 材料科學與工程學系 | - |
| dc.date.embargo-lift | N/A | - |
| Appears in Collections: | 材料科學與工程學系 | |
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| File | Size | Format | |
|---|---|---|---|
| ntu-113-1.pdf Restricted Access | 11.52 MB | Adobe PDF |
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