Assembly of Two-Dimensional δ-V2O5-Ti3C2Tx Heterostructure Electrodes for Li-Ion Batteries
Authors: Zhang Raymond , Averianov Timofey , Pomerantseva Ekaterina 
Published: November 2022

The bilayered phase of vanadium oxide (δ-V2O5∙nH2O or BVO) synthesized via sol-gel synthesis method is an attractive candidate to be used as a cathode material for Li-ion batteries (LIBs) due to its expanded interlayer spacing, and high theoretical capacity. However, poor electrical conductivity and rapid capacity fade present challenges for achieving high-rate performance and good cycle life during cycling in LIBs. A viable solution to mitigating these drawbacks is to fabricate two-dimensional (2D) heterostructures comprised of vanadium oxide and an additional selected 2D material. Titanium carbide (Ti3C2Tx) MXenes are particularly of interest for their high electronic conductivity (103 S cm-1) and well developed delamination protocols. Herein, we present a wet-based approach for assembling BVO and MXene nanoflakes into 2D heterostructures in suspension.
In this study, we first demonstrate a simple liquid phase exfoliation technique utilizing probe ultrasonication to exfoliate bulk -LixV2O5·nH2O (LVO). Previous experiments from our group showed the exfoliation technique in n-methyl-2-pyrrolidone, an organic solvent that is toxic, flammable, and resulted in low yield during exfoliation. Here, for the first time, we have successfully performed exfoliation of LVO in aqueous media and obtained few layered nanoflakes with high yield after centrifugation. Despite the partial solubility of vanadium oxide in water, these nanoflakes suspended in aqueous media maintained chemical stability and readily assembled into a free-standing film using vacuum filtration. The LVO nanoflake films have a two-dimensional (2D) layered morphology as confirmed by SEM and maintain the bilayered structure as confirmed by XRD.
Due to the hydrated nature of LVO, we also highlight the importance of controlling interlayer water content with vacuum drying for achieving better cycling stability. The comparison of a 105°C and 200°C vacuum drying temperature and corresponding interlayer water content was carried out using XRD, TGA, and Raman spectroscopy characterization methods. The 200°C vacuum dried LVO nanoflake cathode achieved an initial ion storage capacity of 212 mAh g-1 which was 32.5% higher than the sample dried at 105°C. In addition, galvanostatic cycling experiments conducted for the 200°C vacuum dried LVO nanoflake cathode show there were significant improvements in capacity retention by ~35%, compared to the 105°C dried sample, after 100 cycles at a current density of 20 mA g-1.
Subsequently, dispersions of LVO and Ti3C2Tx flakes in water were combined in different weight ratios of 9:1, 4:1, and 1:1 LVO to Ti3C2Tx. The heterostructure electrostatic assembly was facilitated by the introduction of a cationic species into the mixed suspensions. Resistivity measurements showed that heterostructure films achieved electronic conductivities as high as ~105 higher than pristine LVO. Through electrochemical testing, the 9:1 heterostructure cathodes delivered the highest ion storage capacity of 167 mAh g-1. At the cost of lower capacity (125.3 mAh g-1), the 4:1 heterostructures maintain a superior capacity retention of ~96% after 10 cycles. Furthermore, rate capability experiments for the 9:1 heterostructure cathodes demonstrate that the addition of 10 wt % Ti3C2Tx to LVO enables greater tolerance to high current densities with a capacity retention of ~90% after cycling through increasing current densities. In this work we also show that increased capacities can be acquired upon the extension of the potential window below 2V covering where Ti3C2Tx exhibits redox activity.
These results demonstrate an environmentally friendly and safe approach to obtaining 2D LVO nanoflakes and offers pathways to constructing novel vanadium oxide based 2D heterostructures for improving electrochemical performance in energy storage devices.