Electronic Structure Modulation in MoO2/MoP Heterostructure to Induce Fast Electronic/Ionic Diffusion Kinetics for Lithium Storage

Transition metal oxides (TMOs) are considered as the prospective anode materials in lithium-ion batteries (LIBs). Nevertheless, the disadvantages, including large volume variation and poor electrical conductivity, obstruct these materials to meet the needs of practical application. Well-designed mesoporous nanostructures and electronic structure modulation can enhance the electron/Li-ions diffusion kinetics. Herein, a unique mesoporous molybdenum dioxide/molybdenum phosphide heterostructure nanobelts (meso-MoO2/MoP-NBs) composed of uniform nanoparticles is obtained by one-step phosphorization process. The Mott-Schottky tests and density functional theory calculations demonstrated that meso-MoO2/MoP-NBs possesses superior electronic conductivity. The detailed lithium storage mechanism (solid solution reaction for MoP and partial conversion for MoO2), small change ratio of crystal structure and fast electronic/ionic diffusion behavior of meso-MoO2/MoP-NBs are systematically investigated by operando X-ray diffraction, ex situ transmission electron microscopy, and kinetic analysis. Benefiting from the synergistic effects, the meso-MoO2/MoP-NBs displays a remarkable cycling performance (515 mAh g(-1) after 1000 cycles at 1 A g(-1)) and excellent rate capability (291 mAh g(-1) at 8 A g(-1)). These findings can shed light on the behavior of the electron/ion regulation in heterostructures and provide a potential route to develop high-performance lithium-ion storage materials.

Automated summary

This study investigates the performance of a heterostructure nanobelt material composed of mesoporous molybdenum dioxide and molybdenum phosphide. By designing the structure and modulating the electronic properties, the material demonstrates improved electrical conductivity and electron/Li-ions diffusion kinetics. Through experiments and calculations, the lithium storage mechanism, crystal structure changes, and diffusion behavior are characterized. The material exhibits excellent cycling performance and rate capability, offering a potential avenue for developing high-performance lithium-ion storage materials.