Issue 1, 2017

Improved Li-ion diffusion and stability of a LiNi0.5Mn1.5O4 cathode through in situ co-doping with dual-metal cations and incorporation of a superionic conductor

Abstract

The co-doping with metal cations and incorporation of the Li7La3Zr2O12 (LLZO) superionic conductor into spinel LiNi0.5Mn1.5O4 are achieved in situ through a spray drying method by co-doping with Zr and La elements. Microscopic structural characterizations reveal that the doping of hetero-cations into LiNi0.5Mn1.5O4 is effective at reducing the amount of Mn3+, enhancing the cation ordering, and improving the structural stability of LNMO crystals. Scanning transmission electron microscopy (STEM) and Energy Dispersive Spectrometric (EDS) analyses validate the successful growth of LLZO during the calcination of the LNMO material. Incorporation of the LLZO superionic conductor into the bulk phase of LNMO considerably improves the intrinsic lithium diffusion rate within the crystal. Electrochemical studies reveal that the LNMO/LLZO composite at 50 : 1 ratio exhibits the best overall electrochemical behavior, in terms of reversible capacity, rate capability, and long-term cycling performance. At 20C discharge rate, the composite cathode delivers a capacity of 84.5 mA h g−1, whereas the pristine LNMO only maintains 14.8 mA h g−1 capacity. After 300 cycles, a capacity retention of 95.9% is obtained for the composite electrode, but only 87.6% for the pure LNMO cathode. The lithium ion diffusion coefficient of 1.83 × 10−10 cm2 s−1 is obtained for the composite cathode, which is three times as high as that of pure LNMO (6.43 × 10−11).

Graphical abstract: Improved Li-ion diffusion and stability of a LiNi0.5Mn1.5O4 cathode through in situ co-doping with dual-metal cations and incorporation of a superionic conductor

Article information

Article type
Paper
Submitted
13 Oct 2016
Accepted
02 Nov 2016
First published
02 Nov 2016

J. Mater. Chem. A, 2017,5, 145-154

Improved Li-ion diffusion and stability of a LiNi0.5Mn1.5O4 cathode through in situ co-doping with dual-metal cations and incorporation of a superionic conductor

W. Liu, Q. Shi, Q. Qu, T. Gao, G. Zhu, J. Shao and H. Zheng, J. Mater. Chem. A, 2017, 5, 145 DOI: 10.1039/C6TA08891K

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