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Destructive gas generation with associated swelling has been a major challenge to the large-scale application of lithium ion batteries (LIBs) made from Li₄Ti₅O₁₂ (LTO) anodes. Here we report root causes of the gassing behavior and suggest remedy to suppress it. The generated gases mainly contain H₂, CO₂ and CO, which originate from interfacial reactions between LTO and surrounding alkyl carbonate solvents. The reactions occur at the very thin outermost surface of LTO (111) plane, which result in transformation from (111) to (222) plane and formation of (101) plane of anatase TiO₂. A nanoscale carbon coating along with a stable solid electrolyte interface (SEI) film around LTO is seen most effective as a barrier layer in suppressing the interfacial reaction and resulting gassing from the LTO surface. Such an ability to tune the interface nanostructure of electrodes has practical implications in the design of next …