The synergic effects of Ca and Sm co-doping on the crystal structure and electrochemical performances of Li4-xCaxTi5-xSmxO12 anode material |
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| Institution: | 1. Department of Nuclear Physics, China Institute of Atomic Energy, Beijing, 102413, China;2. College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing, 100049, China;3. State Key Laboratory for Mesoscopic Physics, School of Physics, Peking University, Beijing, 100871, China;1. Department of Physics, Andhra University, Visakhapatnam 530003, India;2. Department of Physics, Dr. B. R. Ambedkar University, Srikakulam 532410, India;3. Department of Nuclear Physics, Andhra University, Visakhapatnam 530003, India;4. Department of ECE, Aditya College of Engineering and Technology, Kakinada 533005, India;1. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, PR China;2. College of Chemistry and Materials Science, Hebei Normal University, Shijiazhuang, Hebei 050024, PR China;1. ?ukasiewicz Research Network - Institute of Electronic Materials Technology, Wólczyńska 133, 01-919, Warsaw, Poland;2. Department of Chemistry, V?B-Technical University of Ostrava, 17. listopadu 15/2172, 708 00, Ostrava-Poruba, Czech Republic;3. Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okólna 2, 50-950, Wroc?aw, Poland;4. Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw, Poland;5. ?ukasiewicz Research Network - Electrotechnical Institute, Division of Electrotechnology and Materials Science, M. Sk?odowskiej-Curie 55/61, 50-369, Wroclaw, Poland;6. Active Students Association, SEP Branch No. 1 in Wroc?aw, M. Sk?odowskiej-Curie 55/61, 50-369, Wroc?aw, Poland;7. Wroclaw University of Science and Technology, Faculty of Microsystem Electronics and Photonics, Janiszewskiego 11/17, 50-372, Wroc?aw, Poland;8. Faculty of Physics, University of Warsaw, Pasteura 5, 02-093, Warsaw, Poland;9. Department of Biophysics and Human Physiology, Medical University of Warsaw, Cha?ubinskiego 5, 02-004, Warsaw, Poland;1. Department of Metallurgical and Materials Engineering, Indian Institute of Technology Roorkee-247667, India;2. School of Electronics & Electrical Engineering, Lovely Professional University, Punjab-144411,India |
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| Abstract: | Li4Ti5O12 as the well-known “zero strain” anode material for lithium ion batteries (LIBs) suffers from low intrinsic ionic and electronic conductivity. The strategy of lattice doping has been widely taken to relieve the intrinsic issues. But the roles of the dopants are poorly understood. Herein, we propose to modulate the crystal structure and improve the electrochemical performance of Li4Ti5O12 by substituting Li and Ti with Ca and Sm, respectively. The roles of Ca and Sm on the crystal structure and electrochemical performances have been comprehensively investigated by means of X-ray diffraction (XRD), neutron diffraction (ND) and electrochemical analysis. The Rietveld refinement of ND data indicate that Ca and Sm prefer to take 8a site (tetrahedral site) and 16d site (octahedral site), respectively. Li3.98Ca0.02Ti4.98Sm0.02O12 has the longer Li1-O bond and shorter Ti-O bond length which reduces Li+ migration barrier as well as enhances the structure stability. Ca-Sm co-doping also alleviates the electrode polarization and enhances the reversibility of oxidation and reduction. In compared to bare Li4Ti5O12 and Li3.95Ca0.05Ti4.95Sm0.05O12, Li3.98Ca0.02Ti4.98Sm0.02O12 electrode shows the lower charge transfer resistance, higher Li+ diffusion coefficient, better rate capability and cycling performance. The proposed insights on the roles of dopants are also instructive to design high performance electrode materials by lattice doping. |
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| Keywords: | Lithium ion battery Anode Co-doping Neutron diffraction |
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