Co-solvent Engineering for Improved Stability of the Ti3C2Tx Zn-free Anode

Abstract

With the depletion of energy resources and escalating environmental issues, the development of new energy sources and advanced energy storage devices has become increasingly critical. Zinc-ion batteries have attracted significant attention due to their lower cost and safer chemistry. A major focus of zinc-ion battery research is the development of zinc anodes and electrolyte design. Zinc-free anodes have emerged as a promising strategy, offering higher zinc utilization compared to traditional zinc metal anodes (approximately 10%). Among many zinc-free anodes, Ti₃C₂Tx, a MXene (transition metal nitride/carbide layered material), stands out due to its lower lattice mismatch (~10%), higher conductivity, superior mechanical properties, and good hydrophilicity. However, the higher zinc utilization of zinc-free anodes presents challenges for the stable plating/stripping of zinc. Co-solvent engineering is a convenient and direct approach to improving the stability of zinc-free anodes.

In this study, we propose the use of PEG and IPA as co-solvents added to a 1M Zn(OTF)₂-H₂O electrolyte to enhance the stability of Ti₃C₂Tx zinc-free anodes. We found that the addition of PEG reduced the hydrogen evolution current by 0.42 mA (at -1.3 V vs. Ag wire), indicating suppression of the hydrogen evolution reaction. Furthermore, the addition of PEG in the electrolyte inhibits the 2D diffusion of zinc on the Ti₃C₂ surface and promotes zinc deposition along the (002) crystal direction, increasing the (002)/(001) ratio from 0.59 to 0.86, leading to more uniform zinc deposition. Consequently, the Ti₃C₂ zinc-free anode achieved a coulombic efficiency of 97.67% and a cycle life of 268 hours. Similarly, the addition of IPA reduced the hydrogen evolution current by 0.39 mA (at -1.3 V vs. Ag wire), indicating a weaker hydrogen evolution reaction. Moreover, the addition of IPA in the electrolyte inhibits 2D diffusion on the Ti₃C₂ surface and facilitates zinc deposition along the (002) crystal direction, increasing the (002)/(001) ratio from 0.59 to 0.87. The formation of an SEI containing ZnCO₃, ZnFx, and F-rich organics helps to homogenize the Zn ion gradient. Ultimately, the Ti₃C₂ zinc- free anode achieved a high coulombic efficiency of 98.95% and a cycle life of over 1200 hours in the IPA-containing electrolyte.