Lithium cobalt oxide (LCO) is a widely used cathode material for lithium-ion batteries. However, it suffers from irreversible phase transition during cycling because of high cutoff voltage or huge concentration polarization in thick electrode, resulting in deteriorated cyclability. Here, we design a low tortuous LiCoO2 (LCO-LT) electrode by ice-templating method and investigate the reversibility of LCO phase transition. LCO-LT thick electrode shows accelerated lithium-ion transport and reduced concentration polarization, achieving excellent rate capability and homogeneous actual operating voltage. Moreover, LCO-LT thick electrode exhibits a durable phase transition between O2 and H1–3, mitigated volume expansion, and suppressed microcrack formation. LCO-LT electrode (25 mg cm–2) delivers improved capacity retentions of 94.4% after 200 cycles and 93.3% after 150 cycles at cutoff voltages of 4.3 and 4.5 V, respectively. This strategy provides a new concept to improve the reversibility of LCO phase transition in thick electrode by low tortuosity design.

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