Protons Enhance Conductivities in Lithium Halide Hydroxide/Lithium Oxyhalide Solid Electrolytes by Forming Rotating Hydroxy Groups

被引:79
作者
Song, Ah-Young [1 ]
Xiao, Yiran [1 ]
Turcheniuk, Kostiantyn [1 ]
Upadhya, Punith [1 ]
Ramanujapuram, Anirudh [1 ]
Benson, Jim [1 ]
Magasinski, Alexandre [1 ]
Olguin, Marco [2 ]
Meda, Lamartine [3 ]
Borodin, Oleg [2 ]
Yushin, Gleb [1 ]
机构
[1] Georgia Inst Technol, Sch Mat Sci & Engn, Atlanta, GA 30332 USA
[2] Army Res Lab, SEDD, Electrochem Branch, Adelphi, MD 20783 USA
[3] Xavier Univ Louisiana, Dept Chem, New Orleans, LA 70125 USA
关键词
antiperovskite; Li-ion conductivity; molecular dynamics simulations; solid state electrolyte; X-ray diffraction; RICH ANTI-PEROVSKITE; IONIC-CONDUCTIVITY; LI3OCL; STABILITY; TRANSPORT;
D O I
10.1002/aenm.201700971
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Li-halide hydroxides (Li2OHX) and Li-oxyhalides (Li3OX) have emerged as new classes of low-cost, lightweight solid state electrolytes (SSE) showing promising Li-ion conductivities. The similarity in the lattice parameters between them, careless synthesis, and insufficient rigor in characterization often lead to erroneous interpretations of their compositions. Finally, moisture remaining in the synthesis or cell assembling environment and variability in the equivalent circuit models additionally contribute to significant errors in their properties. Thus, there remains a controversy about the real values of Li-ion conductivities in such SSEs. Here an ultra-fast synthesis and comprehensive material characterization is utilized to report on the ionic conductivities of contaminant-free Li2+xOH(1-x)Cl (x=0-0.7), and Li2OHBr not exceeding 10(-4) S cm(-1) at 110 degrees C. Using powerful combination of experimental and numerical approaches, it is demonstrated that the presence of H in these SSEs yields significantly higher Li+ -ionic conductivity. Born-Oppenheimer molecular dynamics simulations show excellent agreement with experimental results and reveal an unexpected mechanism for faster Li+ transport. It involves rotation of a short OH-group in SSEs, which opens lower-energy pathways for the formation of Frenkel defects and highly-correlated Li+ jumps. These findings will reduce the existing confusions and show new avenues for tuning SSE compositions for further improved Li-ion conductivities.
引用
收藏
页数:11
相关论文
共 34 条
  • [1] Novel Li3ClO based glasses with superionic properties for lithium batteries
    Braga, M. H.
    Ferreira, J. A.
    Stockhausen, V.
    Oliveira, J. E.
    El-Azab, A.
    [J]. JOURNAL OF MATERIALS CHEMISTRY A, 2014, 2 (15) : 5470 - 5480
  • [2] Canonical sampling through velocity rescaling
    Bussi, Giovanni
    Donadio, Davide
    Parrinello, Michele
    [J]. JOURNAL OF CHEMICAL PHYSICS, 2007, 126 (01)
  • [3] Anharmonicity and phase stability of antiperovskite Li3OCl
    Chen, Min-Hua
    Emly, Alexandra
    Van der Ven, Anton
    [J]. PHYSICAL REVIEW B, 2015, 91 (21):
  • [4] Rational Composition Optimization of the Lithium-Rich Li3OCl1-xBrx Anti-Perovskite Superionic Conductors
    Deng, Zhi
    Radhakrishnan, Balachandran
    Ong, Shyue Ping
    [J]. CHEMISTRY OF MATERIALS, 2015, 27 (10) : 3749 - 3755
  • [5] Orientational disorder in perovskite like structures of Li2X(OD) (X=Cl, Br) and LiBr center dot D2O
    Eilbracht, C
    Kockelmann, W
    Hohlwein, D
    Jacobs, H
    [J]. PHYSICA B, 1997, 234 : 48 - 50
  • [6] Phase Stability and Transport Mechanisms in Antiperovskite Li3OCl and Li3OBr Superionic Conductors
    Emly, Alexandra
    Kioupakis, Emmanouil
    Van der Ven, Anton
    [J]. CHEMISTRY OF MATERIALS, 2013, 25 (23) : 4663 - 4670
  • [7] Separable dual-space Gaussian pseudopotentials
    Goedecker, S
    Teter, M
    Hutter, J
    [J]. PHYSICAL REVIEW B, 1996, 54 (03) : 1703 - 1710
  • [8] A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
    Grimme, Stefan
    Antony, Jens
    Ehrlich, Stephan
    Krieg, Helge
    [J]. JOURNAL OF CHEMICAL PHYSICS, 2010, 132 (15)
  • [9] Relativistic separable dual-space Gaussian pseudopotentials from H to Rn
    Hartwigsen, C
    Goedecker, S
    Hutter, J
    [J]. PHYSICAL REVIEW B, 1998, 58 (07) : 3641 - 3662
  • [10] Glass-amorphous alkali-ion solid electrolytes and their performance in symmetrical cells
    Helena Braga, M.
    Murchison, Andrew J.
    Ferreira, Jorge A.
    Singh, Preetam
    Goodenough, John B.
    [J]. ENERGY & ENVIRONMENTAL SCIENCE, 2016, 9 (03) : 948 - 954