TY - JOUR
T1 - Liquid-Like Li-Ion Conduction in Oxides Enabling Anomalously Stable Charge Transport across the Li/Electrolyte Interface in All-Solid-State Batteries
AU - Wu, Jian Fang
AU - Zou, Zheyi
AU - Pu, Bowei
AU - Ladenstein, Lukas
AU - Lin, Shen
AU - Xie, Wenjing
AU - Li, Shen
AU - He, Bing
AU - Fan, Yameng
AU - Pang, Wei Kong
AU - Wilkening, H. Martin R.
AU - Guo, Xin
AU - Xu, Chaohe
AU - Zhang, Tao
AU - Shi, Siqi
AU - Liu, Jilei
N1 - Publisher Copyright:
© 2023 Wiley-VCH GmbH.
PY - 2023/10/5
Y1 - 2023/10/5
N2 - The softness of sulfur sublattice and rotational PS4 tetrahedra in thiophosphates result in liquid-like ionic conduction, leading to enhanced ionic conductivities and stable electrode/thiophosphate interfacial ionic transport. However, the existence of liquid-like ionic conduction in rigid oxides remains unclear, and modifications are deemed necessary to achieve stable Li/oxide solid electrolyte interfacial charge transport. In this study, by combining the neutron diffraction survey, geometrical analysis, bond valence site energy analysis, and ab initio molecular dynamics simulation, 1D liquid-like Li-ion conduction is discovered in LiTa2PO8 and its derivatives, wherein Li-ion migration channels are connected by four- or five-fold oxygen-coordinated interstitial sites. This conduction features a low activation energy (0.2 eV) and short mean residence time (<1 ps) of Li ions on the interstitial sites, originating from the Li–O polyhedral distortion and Li-ion correlation, which are controlled by doping strategies. The liquid-like conduction enables a high ionic conductivity (1.2 mS cm−1 at 30 °C), and a 700 h anomalously stable cycling under 0.2 mA cm−2 for Li/LiTa2PO8/Li cells without interfacial modifications. These findings provide principles for the future discovery and design of improved solid electrolytes that do not require modifications to the Li/solid electrolyte interface to achieve stable ionic transport.
AB - The softness of sulfur sublattice and rotational PS4 tetrahedra in thiophosphates result in liquid-like ionic conduction, leading to enhanced ionic conductivities and stable electrode/thiophosphate interfacial ionic transport. However, the existence of liquid-like ionic conduction in rigid oxides remains unclear, and modifications are deemed necessary to achieve stable Li/oxide solid electrolyte interfacial charge transport. In this study, by combining the neutron diffraction survey, geometrical analysis, bond valence site energy analysis, and ab initio molecular dynamics simulation, 1D liquid-like Li-ion conduction is discovered in LiTa2PO8 and its derivatives, wherein Li-ion migration channels are connected by four- or five-fold oxygen-coordinated interstitial sites. This conduction features a low activation energy (0.2 eV) and short mean residence time (<1 ps) of Li ions on the interstitial sites, originating from the Li–O polyhedral distortion and Li-ion correlation, which are controlled by doping strategies. The liquid-like conduction enables a high ionic conductivity (1.2 mS cm−1 at 30 °C), and a 700 h anomalously stable cycling under 0.2 mA cm−2 for Li/LiTa2PO8/Li cells without interfacial modifications. These findings provide principles for the future discovery and design of improved solid electrolytes that do not require modifications to the Li/solid electrolyte interface to achieve stable ionic transport.
KW - distorted polyhedra
KW - interfacial ionic transport
KW - liquid-like conduction
KW - oxide solid electrolytes
UR - http://www.scopus.com/inward/record.url?scp=85167701847&partnerID=8YFLogxK
U2 - 10.1002/adma.202303730
DO - 10.1002/adma.202303730
M3 - Article
AN - SCOPUS:85167701847
SN - 0935-9648
VL - 35
JO - Advanced Materials
JF - Advanced Materials
IS - 40
M1 - 2303730
ER -