Dual-Defect Engineering Strategy Enables High-Durability Rechargeable Magnesium-Metal Batteries

doi:10.1007/s40820-024-01410-8

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Abstract

Rechargeable magnesium-metal batteries (RMMBs) are promising next-generation secondary batteries; however, their development is inhibited by the low capacity and short cycle lifespan of cathodes. Although various strategies have been devised to enhance the Mg²⁺ migration kinetics and structural stability of cathodes, they fail to improve electronic conductivity, rendering the cathodes incompatible with magnesium-metal anodes. Herein, we propose a dual-defect engineering strategy, namely, the incorporation of Mg²⁺ pre-intercalation defect (P-Mg_d) and oxygen defect (O_d), to simultaneously improve the Mg²⁺ migration kinetics, structural stability, and electronic conductivity of the cathodes of RMMBs. Using lamellar V₂O₅·nH₂O as a demo cathode material, we prepare a cathode comprising Mg_0.07V₂O₅·1.4H₂O nanobelts composited with reduced graphene oxide (MVOH/rGO) with P-Mg_d and O_d. The O_d enlarges interlayer spacing, accelerates Mg²⁺ migration kinetics, and prevents structural collapse, while the P-Mg_d stabilizes the lamellar structure and increases electronic conductivity. Consequently, the MVOH/rGO cathode exhibits a high capacity of 197 mAh g⁻¹, and the developed Mg foil//MVOH/rGO full cell demonstrates an incredible lifespan of 850 cycles at 0.1 A g⁻¹, capable of powering a light-emitting diode. The proposed dual-defect engineering strategy provides new insights into developing high-durability, high-capacity cathodes, advancing the practical application of RMMBs, and other new secondary batteries.

Key words： Rechargeable magnesium-metal batteries Dual-defect engineering Vanadium-based cathode High durability Lamellar structure

Received: 30 January 2024 Published: 29 April 2024

Corresponding Authors: Hong-Yi Li, Fusheng Pan

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	Fuyu Chen
	Bai-Qing Zhao
	Kaifeng Huang
	Xiu-Fen Ma
	Hong-Yi Li
	Xie Zhang
	Jiang Diao
	Jili Yue
	Guangsheng Huang
	Jingfeng Wang
	Fusheng Pan

Cite this article:

Fuyu Chen,Bai-Qing Zhao,Kaifeng Huang, et al. Dual-Defect Engineering Strategy Enables High-Durability Rechargeable Magnesium-Metal Batteries[J]. Nano-Micro Letters, 2024, 16(1): 184-.

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https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01410-8 OR https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/184

Fig. 1 Characterization of MVOH/rGO. a Rietveld refinement of the XRD pattern. b, c SEM and TEM images. d EDS spectrum. e Lamellar crystal structure. f Partial density of states (PDOS) for V2O5·nH2O with P-Mgd. g PDOS for V2O5·nH2O without the defects. h, i HRTEM image and corresponding IFFT image

Fig. 2 Verification of Od in MVOH/rGO. a, b Atomic-resolution HAADF-STEM images and corresponding structural illustration. c EPR spectra of MVOH and MVOH/rGO. d-f High-resolution XPS spectra of O 1s at different etching depths. g-i High-resolution XPS spectra of V 2p at different etching depths

Fig. 3 a CV curves of MVOH/rGO, MVOH, and VOH at 1.0 mV s−1. b GCD curves of MVOH/rGO at 0.02-3.0 A g−1. c Rate performance of MVOH/rGO at 0.02-3.0 A g−1. d GCD curves of VOH at 0.02 A g−1. e, f Rate performance and corresponding GCD curves of MVOH. g GCD curves of MVOH/rGO in the initial three cycles at 0.02 A g−1. h Long-term cycle performance of MVOH/rGO at 1 A g-1

Fig. 4 Charge-storage mechanism of the MVOH/rGO cathode. a CV curves at scan rates of 0.1-0.8 mV s−1. b Capacitive and diffusion contribution ratio at 0.1-0.8 mV s−1. c EIS spectrum. d GCD profiles at 0.02 A g−1. e Ex situ XRD spectra at different charge/discharge states (A-F). f HRTEM images obtained in different charge-discharge states. g, h High-resolution ex situ XPS spectra of V 2p and Mg 1s in fully charged, fully discharged, and pristine states

Fig. 5 Electrochemical performance of the Mg foil//MVOH/rGO full cell. a Schematic of the cell. b GCD curves at a current density of 0.02-1.0 A g−1. c Rate performance. d Long-term cycle performance at 0.1 A g−1, Inset: powering an orange LED. e Comparison results of the cycle lifespan

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