Understanding fast ion dynamics in sodiated Li4Na x Ti5O12: from interfacial to extended Li+ and Na+ dynamics in its mixed-conducting solid solutions

被引:3
作者
Posch, Patrick [1 ]
Lunghammer, Sarah [1 ]
Wilkening, Alexandra [1 ]
Hogrefe, Katharina [1 ]
Wilkening, H. Martin R. [1 ]
机构
[1] Graz Univ Technol, Inst Chem & Technol Mat NAWI Graz, Stremayrgasse 9, A-8010 Graz, Austria
来源
JOURNAL OF PHYSICS-ENERGY | 2023年 / 5卷 / 01期
关键词
NMR; Li4Ti5O12; sodiation; solid solution; ion dynamics; activation energies; SPIN-LATTICE-RELAXATION; LITHIUM-ION; DIFFUSION PARAMETERS; SODIUM STORAGE; ANODE MATERIAL; LI-7; NMR; INSERTION; BATTERY; ELECTRODE; MECHANISM;
D O I
10.1088/2515-7655/ac9d03
中图分类号
TE [石油、天然气工业]; TK [能源与动力工程];
学科分类号
0807 ; 0820 ;
摘要
Climate change and energy crises require the development of new sustainable materials to realise reliable electrochemical energy storage devices. Spinel-type Li4Ti5O12 (LTO) is one of the most promising anode materials not only for Li-based batteries, but also for those relying on sodium. While Li+ ion dynamics at the early stages of lithiation has been studied already previously, almost no data on the diffusion properties of Na+ ions can be found in the literature. Here, we used nucleus-specific Li-7 and Na-23 nuclear magnetic resonance (NMR) spectroscopy to quantify the motional processes in mixed-conducting Li4Na (x) Ti5O12 with x = 0.1, 0.5 and 1.5 on the angstrom length scale. Most importantly, our results reveal a strong increase in Li+ diffusivity in the early stages of chemical sodiation that is accompanied by a sharp decrease in activation energy when x reaches 0.5. The two-component Li-7 NMR spectra point to the evolution of an interfacial solid solution at very low sodiation levels (x = 0.1). At x = 0.5, these regions emerge over almost the entire crystallite area, enabling rapid 8a-16c-8a Li+ exchange (0.4 eV), which leads to facile long-range ion transport. We direct the attention of the reader towards the initial formation of solid solutions in LTO-based anode materials and their capital impact on overall ion dynamics. In contrast to macroscopic electrochemical testing, NMR is uniquely positioned to detect and to resolve these exceptionally fast ion dynamics during the initial stages of sodiation. As these processes crucially determine the fast-charging performance of LTO-type batteries, our study lays the atomistic foundations to establish a general understanding of why two-phase materials such as LTO can act as an impressive insertion host for both Li and Na ions.
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页数:13
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共 70 条
  • [1] STUDY OF ULTRASLOW ATOMIC MOTIONS BY MAGNETIC RESONANCE
    AILION, D
    SLICHTER, CP
    [J]. PHYSICAL REVIEW LETTERS, 1964, 12 (07) : 168 - &
  • [2] OBSERVATION OF ULTRA-SLOW TRANSLATIONAL DIFFUSION IN METALLIC LITHIUM BY MAGNETIC RESONANCE
    AILION, DC
    SLICHTER, CP
    [J]. PHYSICAL REVIEW, 1965, 137 (1A): : A235 - &
  • [3] Zero-strain insertion mechanism of Li[Li1/3Ti5/3]O for advanced lithium-ion (shuttlecock) batteries
    Ariyoshi, K
    Yamato, R
    Ohzuku, T
    [J]. ELECTROCHIMICA ACTA, 2005, 51 (06) : 1125 - 1129
  • [4] Three-volt lithium-ion battery with Li[Ni1/2Mn3/2]O4 and the zero-strain insertion material of Li[Li1/3Ti5/3]O4
    Ariyoshi, K
    Yamamoto, S
    Ohzuku, T
    [J]. JOURNAL OF POWER SOURCES, 2003, 119 : 959 - 963
  • [5] Building better batteries
    Armand, M.
    Tarascon, J. -M.
    [J]. NATURE, 2008, 451 (7179) : 652 - 657
  • [6] Bertermann R, 1998, Z NATURFORSCH A, V53, P863
  • [7] NMR studies of the lithium dynamics in two thioborate superionic conductors:: Li9B19S33 and Li4-2xSr2+xB10S19 (x≈0.27)
    Bertermann, R
    Müller-Warmuth, W
    Jansen, C
    Hiltmann, F
    Krebs, B
    [J]. SOLID STATE IONICS, 1999, 117 (3-4) : 245 - 255
  • [8] Li Ion Dynamics in Nanocrystalline and Structurally Disordered Li2TiO3
    Brandstaetter, Harald
    Wohlmuth, Dominik
    Bottke, Patrick
    Pregartner, Veronika
    Wilkening, Martin
    [J]. ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY & CHEMICAL PHYSICS, 2015, 229 (09): : 1363 - 1374
  • [9] Dispersed Solid Conductors: Fast Interfacial Li-Ion Dynamics in Nanostructured LiF and LiF:γ-Al2O3 Composites
    Breuer, S.
    Pregartner, V.
    Lunghammer, S.
    Wilkening, H. M. R.
    [J]. JOURNAL OF PHYSICAL CHEMISTRY C, 2019, 123 (09) : 5222 - 5230
  • [10] Rapid Li Ion Dynamics in the Interfacial Regions of Nanocrystalline Solids
    Breuer, S.
    Uitz, M.
    Wilkening, H. M. R.
    [J]. JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 2018, 9 (08): : 2093 - 2097