Boosting the electrochemical performance of LiNi0.6Mn0.2Co0.2O2 through a trace amount of Mg-B co-doping

doi:10.1016/j.jmst.2021.02.023

Abstract

Abstract:

The extended cycle life of cells is often sacrificed at the expense of high specific energy for high-nickel materials. Cation doping is a promising method to build high-nickel cathode with high energy density and long cycle life. Herein, a trace amount of Mg-B co-doping in LiNi_0.6Mn_0.2Co_0.2O₂ (NMC622) is investigated in this work, which shows improved structural and electrochemical stability of 1% Mg-0.5 % B co-doped material at both 30 and 55 °C in coin-cell. Comprehensive chemical composition, structural, and surface analysis are carried out in this paper. It was found that all the selected materials have a similar composition to the target. Moreover, Mg and B doping have different effects on the crystal structural change of NMC622, to be more specific, the c-lattice parameter increases with Mg doping, while the Li⁺/Ni²⁺ mixing content increases when B was incorporated into the lattice. Furthermore, the microstructure of primary particles was changed by B doping significantly as confirmed by the SEM images. There were marginal benefits in terms of structural and electrochemical stability of materials introduced by Mg or B sole doping. In comparison, incorporating a suitable amount of both Mg and B into NMC622, we found the capacity retention of cells was noticeably improved by reducing the impedance growth and preventing cation mixing during cycling. This study demonstrates the importance of co-incorporation of Mg, B, and optimizing the co-dopant content to stabilize NMC622 as cathode for lithium-ion batteries.

Key words: High-nickel cathode, Mg doping, B doping, Mg-B co-doping, Electrochemical performance, Lithium-Ion batteries

Ning Zhang, Ying Li, Yifan Qiao. Boosting the electrochemical performance of LiNi_0.6Mn_0.2Co_0.2O₂ through a trace amount of Mg-B co-doping[J]. J. Mater. Sci. Technol., 2021, 89: 167-178.

Figures/Tables 10

Table 1 ICP-OES data of NMC622, 1% Mg, 1% B, 0.5 % Mg-0.5 % B, and 1% Mg-0.5 % B samples. All by atomic ratio.

Sample ID	Ni		Mn		Co		Mg		B
	Target	Real	Target	Real	Target	Real	Target	Real	Target	Real
NMC622	0.6	0.595	0.2	0.201	0.2	0.204	0	NA	0	NA
1% Mg	0.6	0.589	0.2	0.203	0.19	0.201	0.01	0.007	0	NA
1% B	0.6	0.590	0.2	0.201	0.19	0.203	0	NA	0.01	0.006
0.5 % Mg-0.5 % B	0.6	0.594	0.2	0.195	0.19	0.203	0.005	0.004	0.005	0.004
1% Mg-0.5 % B	0.6	0.593	0.2	0.197	0.185	0.198	0.01	0.008	0.005	0.004

Fig. 1. (a) XRD patterns of NMC622, 1% Mg, 1% B, and 1% Mg-0.5 % B. (b) Expanded view of (018/110) peaks. (c) Expanded view of (003) peaks. (d) Possible surface impurity region from XRD.

Fig. 2. (a) Lattice parameter-a and c, (b) Li+/Ni2+ mixing data of selected samples. (c) Williamson-Hall plots of selected samples. Diffraction angle θ and FWHM are obtained from Rietica, Cu Kα data of each peaks were selected in this study.

Fig. 3. SEM images of (a) NMC622, (b) 1% Mg, (c) 1% B, and (d) 1% Mg-0.5 % B samples.

Fig. 4. XPS spectra of (a) Mg 1s, (b) B 1s, (c) O 1s, and (d) Ni 2p of NMC622, 1% Mg, 1% B, and 1% Mg-0.5 % B samples.

Fig. 5. (a) Voltage versus specific capacity and (b) dQ/dV versus V profiles of NMC622, 1% Mg, 1% B, 0.5 % Mg-0.5 % B, and 1% Mg-0.5 % B. Cells were tested at 30 °C with a current of 10 mA/g.

Fig. 6. (a) Cycle life and (b) normalized capacity retention of selected samples. Cells were cycled at 30 °C with a current of 40 mA/g (except for the initial 2 cycles at 10 mA/g) between 3.0 and 4.4 V vs. Li+/Li. (c, d) Discharge voltage curves of NMC622 and 1% Mg-0.5 % B cells at 3rd, 10th, 20th, 30th, 40th, and 50th cycle. (e, f) Differential capacity curves of NMC622 and 1% Mg-0.5 % B cells at 3rd, 10th, 20th, 30th, 40th, and 50th cycle.

Fig. 7. Nyquist plots of EIS of cells with selected samples (a) before and (c) after 50 cycles, and Zre as a function of ω-1/2 (b) before and (d) after 50 cycles. Impedance was measured at 3.9 V vs. Li+/Li at room temperature.

Fig. 8. (a) Rate performance and (b) cycle life at 55 °C. Cells were tested between 3.0 and 4.4 V vs. Li+/Li at various C-rate in which 1 C equals 180 mA/g. XRD patterns and Rietveld refinement of (c) NMC622, (d) 1% Mg, and (e) 1% Mg-0.5 % B doped samples after cycling at 55 °C at 1 C.

Fig. 9. Schematic illustration of the mechanism of stability improvement of NMC622 by Mg and B co-doping.

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Boosting the electrochemical performance of LiNi_0.6Mn_0.2Co_0.2O₂ through a trace amount of Mg-B co-doping

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