V₆O₁₃ is a promising Li-ion battery cathode material for application in the high temperature oil field environment. The material exhibits a high capacity, and the voltage profile contains several plateaus due to complex and still unresolved transformations.¹ The mechanisms behind the transformations that take place during these voltage plateaus are central to understanding and improving battery performance. In this study we present in situ X-ray diffraction data that highlight an asymmetric six-step discharge and five-step charge process (Figure 1). The Li_xV₆O₁₃ unit cell expands sequentially in c, b, and a directions during discharge and reversely shrinks back during charge. This result sheds light on the high specific capacity of V₆O₁₃ and lays the foundation for this material to be used as a cathode for secondary lithium batteries both at ambient and high temperature.