RESUMO
Metal selenides are promising anode candidates for sodium ion batteries (SIBs) because of their high theoretical capacity, low cost, and environmental friendship. However, the low rate capability at high current density due to its inherent low electrical conductivity and poor cycle stability caused by inevitable volume variations during cycling frustrate its practical applications. Herein, we have developed a simple metallic-organic frameworks (MOFs)-derived selenide strategy to synthesize a series of heterogeneous bimetallic selenides encapsulated within graphene aerogels (GA) as anodes for SIBs. The bimetallic selenides/GA composites have unique structural characteristics that can shorten the migration path for Na+/electrons and accommodate the volume variations via additional void space during cycling. The built-in electric fields induced at the heterointerfaces can greatly reduce the activation energy for rapid charge transfer kinetics and promote the diffusion of Na+/electrons. GA is also beneficial for accommodating the volume variations during cycling and improving conductivity. As an advanced anode for SIBs, the MoSe2-Cu1.82Se@GA with a special porous octahedron can deliver the highest capacity of 444.8 mAh/g at a high rate of 1 A/g even after 1000 cycles among the bimetallic selenides/GA composites.
RESUMO
High-nickel cobalt-free layered cathode is regarded as a highly potential cathode material for the next generation lithium ion batteries (LIBs) because of its high energy density, low cost and environmentally benign. However, the poor cycle performance caused by its intrinsic unstable structure and chemo-mechanical instability frustrates its practical applications. Herein, we have developed a new core-shell high-nickel cobalt-free layered LiNi0.95Mg0.02Al0.03O2@Li2ZrO3 (LZO-NMA9523) cathode for high-performance LIBs. The Li2ZrO3 coating layer firstly helps to suppress and reduce the degree of Li+/Ni2+ cation mixing during the material preparation process. In addition, the Li2ZrO3 coating layer can not only accommodate the volume variations and enhance the electricity of the active materials, but also effectively inhibit the harmful irreversible phase transition during the charging/discharging process, thus greatly stabilizing the structure of the high-nickel cobalt-free cathode. As an advanced cathode for LIBs, the LZO-NMA9523 exhibits an excellent reversible capacity of 146.9 mAh g-1 after 100 cycles at 0.5 C with capacity retention of about 80%. This study provides a possible high-nickel cobalt-free layered cathode material for the next generation LIBs.
RESUMO
Transition metal selenides are promising anode candidates for sodium ion batteries (SIBs) because of their higher theoretical capacity and conductivity than metal oxides. However, the disadvantages of severe capacity degradation and poor magnification performance greatly limit their commercial applications. Herein, we have developed a new hollow bimetallic selenides (CoSe2-ZnSe)@reduced graphene oxide (rGO) composite with abundant heterointerfaces. The rGO could not only alleviate the volume variations of hollow CoSe2-ZnSe microspheres during cycling, but also improve the conductivity of composite. The presence of the heterointerfaces could help to accelerate ionic diffusion kinetics and improve electron transfer, resulting in the improved sodium storage performance. As an advanced anode for SIBs, the CoSe2-ZnSe@rGO exhibits an enhanced initial coulombic efficiency of 75.1% (65.2% of CoSe2@rGO), extraordinary rate capability, and outstanding cycling stability (540.3 mAh/g at 0.2 A/g after 150 cycles, and 395.2 mAh/g at 1 A/g after 600 cycles). The electrochemical mechanism was also studied by kinetic analysis, showing that the charging/discharging process of CoSe2-ZnSe@rGO is mostly related to a capacitive-controlled behavior.
