Construction of cobalt vacancies in cobalt telluride to induce fast ionic/electronic diffusion kinetics for lithium-ion half/full batteries

doi:10.1016/j.jmst.2022.04.011

Abstract

Abstract:

Designing novel electrode materials with unique structures is of great significance for improving the performance of lithium ion batteries (LIBs). Herein, copper-doped Co_1-_xTe@nitrogen-doped carbon hollow nanoboxes (Cu-Co_1-_xTe@NC HNBs) have been fabricated by chemical etching of CuCo-ZIF nanoboxes, followed by a successive high-temperature tellurization process. The as-synthesized Cu-Co_1-_xTe@NC HNBs composite demonstrated faster ionic and electronic diffusion kinetics than the pristine CoTe@NC HNBs electrode. The existence of Co-vacancy promotes the reduction of Gibbs free energy change (∆G_H*) and effectively improves the Li⁺ diffusion coefficient. XPS and theoretical calculations show that performance improvement is ascribed to the electronic interactions between Cu-Co_1-_xTe and nitrogen-doped carbon (NC) that trigger the shift of the p-band towards facilitation of interfacial charge transfer, which in turn helps boost up the lithium storage property. Besides, the proposed Cu-doping-induced Co-vacancy strategy can also be extended to other conversion-type cobalt-based material (CoSe₂) in addition to as-obtained Cu-Co_1-_xSe₂@NC HNBs anodes for long-life and high-capacity LIBs. More importantly, the fabricated LiCoO₂//Cu-Co_1-_xTe@NC HNBs full cell exhibits a high energy density of 403 Wh kg⁻¹ and a power density of 6000 W kg⁻¹. We show that the energy/power density reported herein is higher than that of previously studied cobalt-based anodes, indicating the potential application of Cu-Co_1-_xTe@NC HNBs as a superior electrode material for LIBs.

Key words: MOF-derived material, Cobalt telluride, Cobalt vacancy, Diffusion kinetics, Lithium storage

Lei Hu, Lin Li, Yuyang Zhang, Xiaohong Tan, Hao Yang, Xiaoming Lin, Yexiang Tong. Construction of cobalt vacancies in cobalt telluride to induce fast ionic/electronic diffusion kinetics for lithium-ion half/full batteries[J]. J. Mater. Sci. Technol., 2022, 127: 124-132.

Figures/Tables 6

Fig. 1. (a) Schematic representation of the synthesis of Cu-Co1-xTe@NC HNBs. (b-d) SEM and TEM images of Cu-Co1-xTe@NC HNBs. (e, f) HRTEM images and (g) SAED pattern of Cu-Co1-xTe@NC HNBs. (h-j) Elemental mappings showing the distribution of individual elements (Te, Cu and Co) present in Cu-Co1-xTe@NC HNBs.

Fig. 2. (a) Schematic diagram of copper-doped Co1-xTe structure. (b, c) XRD patterns of CoTe@NC HNBs and Cu-Co1-xTe@NC HNBs. (d) Co 2p spectra, (e) N 1 s spectra and (f) Te 3d spectra of CoTe@NC HNBs and Cu-Co1-xTe@NC HNBs. (g) Nitrogen adsorption and desorption curve of CoTe@NC HNBs and Cu-Co1-xTe@NC HNBs.

Fig. 3. (a) CV curves, (b) charge-discharge profiles, (c) rate performance and (d) cycling stability of CoTe@NC HNBs and Cu-Co1-xTe@NC HNBs electrodes.

Fig. 4. (a) CV curves of the Cu-Co1-xTe@NC HNBs at various scan rates. (b) log(i) vs. log(v) plots at different cathodic/anodic peaks. (c) Capacitive and diffusion controlled capacities contribution ratio at various scan rates. (d) Capacitive controlled contribution at 0.8 mV s?1 of Cu-Co1-xTe@NC HNBs. (e) Nyquist plots of two electrodes before and after cycling (the inset is the proposed equivalent circuit). (f) Z' vs. ω?1/2 plots of two electrodes before and after the cyclic performance. (g) GITT curves of Cu-Co1-xTe@NC HNBs electrode. (h, i) Calculated lithium-ion diffusion coefficient at different lithiation/delithiation states of CoTe@NC HNBs and Cu-Co1-xTe@NC HNBs.

Fig. 5. (a) Energy profile of lithium-ion route through CoTe@NC HNBs and Cu-Co1-xTe@NC HNBs. (b) Differences of electron charge density for CoTe@NC HNBs (left image) and Cu-Co1-xTe@NC HNBs (right image) electrodes. (c) DOS curves of CoTe@NC HNBs and Cu-Co1-xTe@NC HNBs, and their corresponding p-bands. (d) Schematic illustration of Cu-Co1-xTe@NC HNBs electrode with bicontinuous electron/ion transfer routes.

Fig. 6. (a) Schematic illustration of the full cell with the LCO cathode and Cu-Co1-xTe@NC HNBs anode. (b) Cyclic stability of LCO cathode. (c) Rate performance of the LCO//Cu-Co1-xTe@NC HNBs full cell device. (d) A Ragone plot comparing the ED and PD of LCO//Cu-Co1-xTe@NC HNBs full cell with the recently reported cobalt-based full LIBs.

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