Superior lithium storage performance in MoO_(3) by synergistic effects:Oxygen vacancies and nanostructures

Molybdenum trioxide(MoO_(3))has recently attracted wide attention as a typical conversion-type anode of Li-ion batteries(LIBs).Nevertheless,the inferior intrinsic conductivity and rapid capacity fading during charge/discharge process seriously limit large-scale commercial application of MoO_(3).Herein,the density function theory(DFT)calculations show that electron-proton co-doping preferentially bonds symmetric oxygen to form unstable HxMoO_(3).When the-OH-group in HxMoO_(3) is released into the solution in the form of H_(2)O,it is going to form MoO_(3-x)with lower binding energy.By the means of both electron-proton co-doping and high-energy nanosizing,oxygen vacancies and nanoflower structure are introduced into MoO_(3) to accelerate the ion and electronic diffusion/transport kinetics.Benefitting from the promotion of ion diffusion kinetics related to nanostructures,as well as both the augmentation of active sites and the improvement of electrical conductivity induced by oxygen vacancies,the MoO_(3-x)/nanoflower structures show excellent lithium-ion storage performance.The prepared specimen has a high lithium-ion storage capacity of 1261 mA h g^(-1)at 0.1 A g^(-1)and cyclic stability(450 cycle),remarkably higher than those of previously reported MoO_(3)-based anode materials.

Re-delocalization of localized d-electrons in VO_(2)(R)-VS_(4)hetero-structure enables high performance of rechargeable Mg-ion batteries

Rechargeable Mg-ion batteries(MIBs)have attracted much more attentions by virtue of the high capacity from the two electrons chemistry.However,the reversible Mg^(2+)diffusion in cathode materials is restricted by the strong interactions between the high-polarized bivalent Mg^(2+)ions and anionic lattice.Herein,we design and propose a hetero-structural VO_(2)(R)-VS_(4)cathode,in which the re-delocalized d-electrons can effectively shield the polarity of Mg^(2+)ions.Theoretically,the electrons should spontaneously transfer from VS_(4)to VO_(2)(R)through the interfaces of hetero-structure due to the lower work function value of VS_(4).Furthermore,the internal electrons transfer lead to the electronic injection into VO_(2)(R)from VS_(4)and the partially broken V-V dimers,indicating the presence of lone pair electrons and charge re-delocalization.Benefiting from the shield effect of re-delocalized electrons,and the weakened attraction between cations and O/S anions enables more S^(2-)-S_(2)^(2-)redox groups to participate the electrochemical reactions and compensate the double charge of Mg^(2+)ions.Accordingly,VO_(2)(R)-VS_(4)hetero-structure exhibits a high specific capacity of 554 mA h g^(-1)at 50 mA g^(-1).It is believed that the charge re-delocalization of cathode extremely boost the Mg^(2+)ions migration for the high-capacity of MIBs.