Hierarchical Porous Intercalation‐Type V₂O₃ as High‐Performance Anode Materials for Li‐Ion Batteries

Abstract

As intercalation-type anode materials for Li-ion batteries (LIBs), the commercially used graphite and Li Ti O exhibit good cycling and rate properties, but their theoretical specific capacities are too low to meet the ever-growing demands of high-energy applications such as electric vehicles. Therefore, the development of new intercalation-type anode materials with larger capacity is very desirable. Herein, we design and synthesize novel 3 D hierarchical porous V O @C micro/nanostructures consisting of crumpled nanosheets, through self-reduction under annealing from the structurally similar VO (B)@C precursors without the addition of any other reducing reagent or gas. Excitingly, it is found for the first time through ex situ XRD technology that V O is a new, promising intercalation-type anode material for LIBs with a high capacity. V O @C micro/nanostructures can deliver a large capacity of 732 mAh g without capacity loss at 100 mA g even after 136 cycles, as well as exhibiting excellent cycling and rate performances. The application of V O for Na-ion batteries (NIBs) is elaborated for the first time, and excitingly, it is found that V O @C micro/nanostructures may be promising anode materials for NIBs.

Recent Progress in the Applications of Vanadium‐Based Oxides on Energy Storage: from Low‐Dimensional Nanomaterials Synthesis to 3D Micro/Nano‐Structures and Free‐Standing Electrodes Fabrication

“…Another homologous V 2 O 3 /C box-in-box micro/nano-structure was synthesized by a template-assisted hydrothermal method based on a hollow carbon micro-box, as shown in Figure 13. [33] Also, a hierarchical porous V 2 O 5 @C micro/nano-structure with similar structures was synthesized by a in situ oxidizing method through annealing under Air, as shown in Figure 14b. They can deliver a high reversible capacity of 641 mA h g −1 even after 1200 cycles at 1000 mA g −1 , Even when cycled at a large current density of 5000 mA g −1 , a capacity of over 400 mA g −1 was obtained.…”

“…[79] This kind of box-in-box V 2 O 3 /C micro/nanostructures exhibited the excellent long cycling and high rate performances as anode materials of LIBs. [33] Copyright 2017, Wiley. Furthermore, when fabricated as a full cell with taking V 2 O 5 box as cathode materials, a stable capacity was also obtained.…”

“…[72] When applied as cathode materials of NIBs, the V 2 O 5 hollow nanospheres delivered a reversible specific discharge capacity of ≈150 mA h g −1 , which is equal to one Na ion insertion per V 2 O 5 formula unit. Even at high current densities, they also still delivered high capacity and superior cyclability ( [29] (231, 74% after 100 at 80) hierarchical V 2 O 5 spheres [165] (271, 89% after 100 at 80) NA V 6 O 13 NA V 6 O 13 micro-flowers [131] (226, 81% after 30 at 160) NA (135,93 after 100 at 100) [31] NA NA VO 2 (B) VO 2 nanosheets [166] (235, ≈77% after 50 at 10) NA GVG [77] (306, 88% after 1500 at 18000) [33] (239, 84% after 35 at 100) NA NaVO 2 Single crystal NaVO 2 [167] (≈120, -) NA NA NaV 2 O 5 NA NaV 2 O 5 mesocrystal [34] (362, 75% after 10 at 150) NA a) [165] When used as anode materials of NIBs, the as-prepared hierarchical V 2 O 5 exhibited a discharge capacity of 271 mA h g −1 at 40 mA g −1 , and 177 mA h g −1 after 100 cycles.…”

“…[33] It was excitingly found that V 2 O 3 @C micro/nano-structures were the promising anode materials of NIBs: the reversible capacity was 239 mA h g -1 , the capacity was stable during the following cycles, and the capacity retention was up to 84% after 35 cycles. Meanwhile, in our recent published works, we had a try to apply V 2 O 3 @C micro/ nano-structures as electrode materials of NIBs, and illustrated the detailed assembly process of NIBs.…”

“…[28] As cathode materials of NIBs, single-crystalline bilayered V 2 O 5 nanobelts can deliver a high capacity of 229 mA h g −1 at 80 mA g −1 . [33] By applying density functional theory (DFT) and electrochemical method, it was revealed that NaV 2 O 5 was a new anode materials of NIBs with a high capacity (≈362 mA h g −1 ). [30,31] It was found that Li 3 VO 4 was a promising insertion anode material for LIBs with a low and safe discharge voltage (≈0.75 V vs Li/Li + in average), and delivered a large capacity (≈323 mA h g −1 ).…”