Solid electrolyte interphase (SEI) plays a critical role in the performance of lithium-ion batteries (LIBs). In contrast to the clear interface between the traditional consecutive electrode materials and SEI, ionic polyoxometalates (POMs) as electrode could bilaterally diffuse with SEI and form a blending interface for superior electrochemical performance. POMs have recently aroused much interest as electrode materials in LIBs due to their structural flexibility, high capacity, and cycling stability. However, the interface evolution between POM-based electrodes and SEI, which is critical for Li+ ion transportation, has rarely been explored. Herein, we choose Li10[V12B18O60H6] (LVB) as an example to investigate the formation and structural evolution of the electrode-electrolyte interface. Time-of-flight secondary ion mass spectrometry together with X-ray photoelectron spectroscopy demonstrates the evolution of a blending layer at the interface containing typical SEI components, a polyanion from LVB and a phosphate anion from decomposition products of LiPF6. In the blending layer, ion migration takes place between the P-related inorganic species and the polyanion during the Li+ insertion/extraction reaction. Such a compatible blending layer favors Li+ transportation and the reversibility of the redox reactions, as supported by a series of electrochemical analyses. This work provides detailed insights into understanding the interface evolution of the LVB electrode and demonstrates the importance of interfacial engineering to induce proper interface layers in the development of high-performance POM-based electrodes for LIBs.
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