Rational construction of hollow nanoboxes for long cycle life alkali metal ion batteries

doi:10.1016/j.jmst.2021.07.007

Abstract

Abstract:

Hollow nanostructures are extremely attractive in energy storage and show broad application prospects. But the preparation method is accompanied by a complicated process. In this article, the CoZn-based hollow nanoboxes with electrochemical synergy are prepared in a simple way. This structure can effectively shorten the transmission distance of ions and electrons, and alleviate the volume expansion during the cycle. In particular, bimetallic oxides are rich in oxygen vacancies, providing more active sites for electrochemical reactions. In addition, the stepwise oxidation-reduction reaction can also improve the volume change of the electrode material. According to the kinetic analysis and density functional theory (DFT) calculation, it is confirmed that the synergistic effect of the bimetallic oxide can accelerate the reaction kinetics. Based on these characteristics, the electrode exhibits stable cycle performance and long cycle life in alkali metal ion batteries, and can provide reversible capacities of 302.1 (LIBs, 2000 cycles), 172.5 (SIBs, 10000 cycles) and 109.6 (PIBs, 5000 cycles) mA hg^-1 at a current density of 1.0 Ag ^-1, respectively. In addition, by assembling (LiCoO₂//CoZn-O₂) and (Na₃V₂(PO₄)₃//CoZn-O₂) full-cells, the practical application value is demonstrated. The sharing of this work introduces a simple way to synthesize hollow nanoboxes, and shows excellent electrochemical performance, which can also be expanded in other areas.

Key words: Hollow nanoboxes, Bimetallic oxides, DFT calculation, Alkali metal ion batteries

Zheng Zhang, Ying Huang, Xiang Li, Zhiming Zhou. Rational construction of hollow nanoboxes for long cycle life alkali metal ion batteries[J]. J. Mater. Sci. Technol., 2022, 102: 46-55.

Figures/Tables 9

Scheme 1. Preparation of hollow nanoboxes.

Fig. 1. FESEM and TEM images of (a, b) CoZn(2:1)-MOF, (c-i) CoZn-O2. (j, k) EDS mapping. (l, m) HRTEM images of CoZn-O2.

Fig. 2. (a) XRD spectra of oxides. (b, c) BET and NLDFT curves of CoZn-O2. XPS spectra of CoZn-O2 (d) Zn 2p, (e) Co 2p and (f) O 1s.

Fig. 3. FESEM and TEM images of CoZn-O2 obtained at (a) 200°C, (b) 350°C, (c) 450°C and (d) 800°C for 2 h in air.

Fig. 4. Electrochemical performance for SIBs: (a) CV curves of CoZn-O2, (b) GCD curves of CoZn-O2, cycle performance of metal oxides at a current density of (c) 0.2 A g-1 and (f) 1.0 A g-1, (d) rate performance, (e) EIS curves, (g) long-term cycling performance of CoZn-O2 at 1.0 A g-1.

Fig. 5. Electrochemical kinetics analysis for SIBs: (a) CV curves at various scan rates, (b) capacitive contributions at 1.0 mV s-1, (c) EIS curves after 1000 cycles at 1.0 A g-1, (e) GITT curves of CoZn-O2 electrode, (f) Na+ diffusion coefficient. FESEM TEM images of CoZn-O2 electrode after cycling at 1.0 A g-1: (g) 1000 cycles, (h) 2000 cycles and (i) 10000 cycles.

Fig. 6. Electrochemical performance for LIBs: (a) GCD curves of CoZn-O2, cycle performance at a current density of (b) 0.2 A g-1 and (d) 1.0 A g-1, (c) rate performance, (e) CV curves at various scan rates, (f) capacitive contributions at 1.0 mV s-1, (g) capacitive contribution at various scan rates, (h) FESEM and (g) TEM images of CoZn-O2 electrode after 2000 cycles at 1.0 A g-1.

Fig. 7. Electrochemical performance for PIBs: (a) GCD curves of CoZn-O2, cycle performance at a current density of (b) 0.1 A g-1 and (d) 0.5 and 1.0 A g-1, (c) rate performance, (e) CV curves at various scan rates, (f) capacitive contributions at 1.0 mV s-1, (g) capacitive contribution at various scan rates, (h) FESEM and (g) TEM images of CoZn-O2 electrode after 5000 cycles at 1.0 A g-1.

Fig. 8. Calculated DOS of (a) ZnO, (b) Co3O4 and (c) CoZn-O2, dashed line corresponds to the position of the Fermi level. (d-e) Comparison of electrochemical performance between our work and previous work. Electrochemical performance of the full-cell, (g) working diagram, (h) LCO//CoZn-O2, (i) NVP//CoZn-O2.

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