Journal
NANO ENERGY
Volume 20, Issue -, Pages 117-125Publisher
ELSEVIER
DOI: 10.1016/j.nanoen.2015.12.004
Keywords
Optimized Ti substitution; d-Orbital hybridization; Full tetrahedron Li2FeSiO4 nanocrystal; Structural stability; Lithium-storage properties
Categories
Funding
- National Natural Science Foundation of China [51372186]
- National Project for EV Batteries (Optimum Nano, Shenzhen) [20121110]
- Guangdong Innovation Team Project [2013N080]
- Shenzhen Science and Technology Research Grant [ZDSY 20130331145131323, CXZZ 20120829172325895, JCYJ 20120614150338154, JCYJ 20140903101633318]
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Full tetrahedron connected structures possess considerable potential as cathodes for lithium-ion batteries (LIBs) due to more lithium storage sites to obtain high specific capacity. However, different from the full octahedron and octahedron/tetrahedron hybrid structures with coplanar or collinear, the tetrahedron network is connected by common vertex, which provokes structural instability and poor electrochemistry performance. Here, using first principles calculations combined with experiments, we found that a heavy distortion and big volume expansion during delithiation for full tetrahedron (LiO4, FeO4 and SiO4 tetrahedra) Li2FeSiO4 nanocrystal lead to phase change or even structure fracture, and the optimized Ti(IV) doped in Fe sites can enhance the coupling effect among the tetrahedra by the strong d-orbital hybridization and like spring to hold these tetrahedra and prohibit structure fracture. Meanwhile, the Ti(IV) doping can also shorten the distance of two adjacent Li sites to decrease the activation barrier for Li-ion diffusion. Furthermore, the n-type doping effect increases the electronic conductivity. This discovery can be extended to other tetrahedron structures as welt, providing a general approach to develop promising next-generation cathode materials for high-energy and long-life lithium ion batteries. (C) 2015 Elsevier Ltd. All rights reserved.
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