Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction

Haodong Liu; Yan Chen; Sunny Hy; Ke An; Subramanian Venkatachalam; Danna Qian; Minghao Zhang; Ying Shirley Meng

doi:10.1002/aenm.201502143

Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction

Haodong Liu, Yan Chen, Sunny Hy, Ke An, Subramanian Venkatachalam, Danna Qian, Minghao Zhang, Ying Shirley Meng

Materials Engineering

Research output: Contribution to journal › Article › peer-review

116 Scopus citations

Abstract

Neutron diffraction under operando battery cycling is used to study the lithium and oxygen dynamics of high Li-rich Li(Li_x _/3Ni_(3/8-3 _x _/8)Co_(1/4- _x _/4)Mn_(3/8+7 _x _/24)O₂ (x = 0.6, HLR) and low Li-rich Li(Li_x _/3Ni_(1/3- _x _/3)Co_(1/3- _x _/3)Mn_(1/3+ _x _/3)O₂ (x = 0.24, LLR) compounds that exhibit different degrees of oxygen activation at high voltage. The measured lattice parameter changes and oxygen position show largely contrasting changes for the two cathodes where the LLR exhibits larger movement of oxygen and lattice contractions in comparison to the HLR that maintains relatively constant lattice parameters and oxygen position during the high voltage plateau until the end of charge. Density functional theory calculations show the presence of oxygen vacancy during the high voltage plateau; changes in the lattice parameters and oxygen position are consistent with experimental observations. Lithium migration kinetics for the Li-rich material is observed under operando conditions for the first time to reveal the rate of lithium extraction from the lithium layer, and transition metal layer is related to the different charge and discharge characteristics. At the beginning of charging, the lithium extraction predominately occurs within the lithium layer. Once the high voltage plateau is reached, the lithium extraction from the lithium layer slows down and extraction from the transition metal layer evolves at a faster rate.

Original language	English
Article number	1502143
Journal	Advanced Energy Materials
Volume	6
Issue number	7
DOIs	https://doi.org/10.1002/aenm.201502143
State	Published - Apr 6 2016

Funding

UCSD's efforts were supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy (DOE) under Contract No. DE-AC02-05CH11231, Subcontract No. 7073923, under the Advanced Battery Materials Research (BMR) Program. The neutron experiments benefited from the SNS user facility, sponsored by the office of Basic Energy Sciences (BES), the Office of Science of the DOE. H.L. acknowledges the financial support from the China Scholarship Council under Award No. 2011631005. Y.C. acknowledges the support from U.S. DOE's Office of Basic Energy Sciences, Material Science and Engineering Division. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which was supported by National Science Foundation grant number ACI-1053575.

Keywords

cathode materials
energy density
lithium dynamics
lithium-ion batteries
neutron diffraction

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10.1002/aenm.201502143

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title = "Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction",

abstract = "Neutron diffraction under operando battery cycling is used to study the lithium and oxygen dynamics of high Li-rich Li(Lix /3Ni(3/8-3 x /8)Co(1/4- x /4)Mn(3/8+7 x /24)O2 (x = 0.6, HLR) and low Li-rich Li(Lix /3Ni(1/3- x /3)Co(1/3- x /3)Mn(1/3+ x /3)O2 (x = 0.24, LLR) compounds that exhibit different degrees of oxygen activation at high voltage. The measured lattice parameter changes and oxygen position show largely contrasting changes for the two cathodes where the LLR exhibits larger movement of oxygen and lattice contractions in comparison to the HLR that maintains relatively constant lattice parameters and oxygen position during the high voltage plateau until the end of charge. Density functional theory calculations show the presence of oxygen vacancy during the high voltage plateau; changes in the lattice parameters and oxygen position are consistent with experimental observations. Lithium migration kinetics for the Li-rich material is observed under operando conditions for the first time to reveal the rate of lithium extraction from the lithium layer, and transition metal layer is related to the different charge and discharge characteristics. At the beginning of charging, the lithium extraction predominately occurs within the lithium layer. Once the high voltage plateau is reached, the lithium extraction from the lithium layer slows down and extraction from the transition metal layer evolves at a faster rate.",

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AB - Neutron diffraction under operando battery cycling is used to study the lithium and oxygen dynamics of high Li-rich Li(Lix /3Ni(3/8-3 x /8)Co(1/4- x /4)Mn(3/8+7 x /24)O2 (x = 0.6, HLR) and low Li-rich Li(Lix /3Ni(1/3- x /3)Co(1/3- x /3)Mn(1/3+ x /3)O2 (x = 0.24, LLR) compounds that exhibit different degrees of oxygen activation at high voltage. The measured lattice parameter changes and oxygen position show largely contrasting changes for the two cathodes where the LLR exhibits larger movement of oxygen and lattice contractions in comparison to the HLR that maintains relatively constant lattice parameters and oxygen position during the high voltage plateau until the end of charge. Density functional theory calculations show the presence of oxygen vacancy during the high voltage plateau; changes in the lattice parameters and oxygen position are consistent with experimental observations. Lithium migration kinetics for the Li-rich material is observed under operando conditions for the first time to reveal the rate of lithium extraction from the lithium layer, and transition metal layer is related to the different charge and discharge characteristics. At the beginning of charging, the lithium extraction predominately occurs within the lithium layer. Once the high voltage plateau is reached, the lithium extraction from the lithium layer slows down and extraction from the transition metal layer evolves at a faster rate.

KW - cathode materials

KW - energy density

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Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction

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