Degradation of electrode particles during cycling is chemo-mechanically coupled and needs to be systematically investigated for the Li-ion battery development. The effect of Li transport pathway on internal stress and crack formation during cycling remains elusive. The opposite effect of cracked, newly exposed active surface on Li transport pathway alteration, accelerating the chemo-mechanical degradation, also remains poorly known. Using operando scanning transmission X-ray microscopy on [100]-oriented LiFePO4 single particles, we demonstrated that lithium insertion from the edge of the non-cracked particle dynamically generate tensile stress within the particle, thereby initiating crack formation during lithiation. The exposed crack surface acts as a Li (de)insertion hotspot, redirecting Li transport pathway and internal stress-fields. Delithiation process induces the Li-poor phase around the crack, creating tensile stress, propagating the crack, and subsequently exposing fresh surface which serves as active hot-spot. On the other hands, lithiation process induces the Li-rich phases around the crack, creating compressive stress and suppressing crack propagation. Phase-field simulations demonstrate chemo-mechanically interactive loop that lithium (de)insertion pathway determines dynamic tensile/compressive stress distribution, which recursively determines (de)insertion pathway. This study offers insights that can help develop high-performance and long-lasting batteries, as well as cycling protocols that suppress crack formation. Figure 1
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