Active site synergy of the mixed-phase cobalt diselenides with slight lattice distortion for highly reversible and stable lithium oxygen batteries

doi:10.1016/j.jmst.2021.02.056

Abstract

Abstract:

Many non-precious metal-based catalysts with high intrinsic activity for catalytic reactions are prone to structural degradation in practical application, which leads to poor stability. In this work, we propose c-CoSe₂/o-CoSe₂ as the oxygen electrode of lithium-oxygen batteries (LOBs) to improve its cycle stability. The heterogeneous interface inside c-CoSe₂/o-CoSe₂ leads to an increase in the covalence bonds between Co and Se ions, which greatly enhances the robustness of the crystal lattice, thereby improving the stability of the catalyst. In addition, the strong interaction between the mixed phases is favorable for adjusting the electron density around the active sites and boosting oxygen electrode kinetics. Moreover, the epitaxial growth of o-CoSe₂ on c-CoSe₂ will cause abundant heterogeneous interfaces and slight lattice distortion along the interfaces, thereby providing sufficient catalytic reaction sites. The DFT calculation results show that the optimized adsorption of intermediates at the heterogeneous interface plays an important role in boosting oxygen electrode reactions and improving the electrochemical performance of LOBs. The experimental results show that LOBs with the c-CoSe₂/o-CoSe₂ electrodes exhibit outstanding performance, including large specific capacity of about 23,878 mA h g^-1, high coulombic efficiency of up to 93.66%, and excellent stability of over 176 cycles (1410 h).

Key words: Li-O₂ battery, Oxygen electrode, Structure design, Lattice distortion, Jahn-Teller effect

Minglu Li, Chaozhu Shu, Anjun Hu, Yu Yan, Miao He, Jianping Long. Active site synergy of the mixed-phase cobalt diselenides with slight lattice distortion for highly reversible and stable lithium oxygen batteries[J]. J. Mater. Sci. Technol., 2021, 92: 159-170.

Figures/Tables 9

Fig. 1. Schematic diagram of preparing heterogeneous c-CoSe2/o-CoSe2.

Fig. 2. Surface morphology characterization of c-CoSe2/o-CoSe2. (a) TEM image; (b, c) HRTEM image; (d) SAED pattern and (e) EDS elemental mapping of c-CoSe2/o-CoSe2.

Fig. 3. Characterization of composition and structure. (a) Co 2p and (b) Se 3d high-resolution XPS spectra of c-CoSe2/o-CoSe2 and c-CoSe2. (c) Raman spectra and (d) UPS spectra of c-CoSe2/o-CoSe2, o-CoSe2 and c-CoSe2. N2 adsorption and desorption isotherms and pore size distribution (inset) of (e) c-CoSe2/o-CoSe2 and (f) c-CoSe2.

Fig. 4. (a) Schematic structure model of c-CoSe2 (100), o-CoSe2 (101) and [c-CoSe2 (100)||o-CoSe2 (101)] interface. (b) Comparison of PDOS and (c) schematic rigid band diagrams of c-CoSe2, and c-CoSe2/o-CoSe2 interfaces.

Fig. 5. Electrochemical performance. (a) The first discharge-charge curves of LOBs based on different electrodes in a voltage window of 2.0-4.5 V with a current density of 500 mA g -1. Rate performance of LOBs with (b) c-CoSe2/o-CoSe2, (c) o-CoSe2 and (d) c-CoSe2 oxygen electrodes at different current densities. (e) Cycling performance of LOBs at 500 mA g -1 with the cut-off capacity of 2000 mA h g -1.

Fig. 6. Morphological characterization of electrodes at different stages. SEM images of (a-c) c-CoSe2/o-CoSe2 oxygen electrodes; (d-f) c-CoSe2 oxygen electrodes and (h-j) o-CoSe2 oxygen electrodes at (a, d, g) pristine stage; (b, e, f) discharged stage and (c, f, i) charged stage.

Fig. 7. (a, b) Raman spectra, (c, d) Li 1 s and (e, f) C 1 s XPS spectra after discharged/charged for (a, c, e) c-CoSe2/o-CoSe2 electrodes and (b, d, f) c-CoSe2 electrodes.

Fig. 8. (a) UV-Vis spectra (inset is the digital image of TiOSO4 solutions immersed with electrodes at different discharge capacities); (b) Lambert-Beer plot for c-CoSe2/o-CoSe2 oxygen electrode.

Fig. 9. Calculated free energy diagrams for the discharge-charge reactions on (a) c-CoSe2, and (b) c-CoSe2/o-CoSe2. (c) Comparison of charge density distribution on pristine c-CoSe2 surface and lattice distortion c-CoSe2/o-CoSe2 surface. Blue, yellow, red and purple balls represent Co atoms, Se atoms, O atoms and Li atoms in c-CoSe2, respectively. Blue, green, yellow and red represent Co atoms, Se atoms, O atoms and Li atoms in c-CoSe2/o-CoSe2. (d) The mechanism diagram of the reversible formation of Li2O2 on the c-CoSe2/o-CoSe2 oxygen electrode.

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