The electrochemical performance of lithium-ion batteries is directly influenced by type of active material as well as its morphology. In order to evaluate the impact of particle morphology in thick-film electrodes, Li(Ni_0.6Mn_0.2Co_0.2)O₂ (NMC 622) cathodes with bilayer structure consisting of two different particle sizes were manufactured and electrochemically characterized in coin cells design. The hierarchical thick-film electrodes were generated by multiple casting using NMC 622 (TA) with small particle size of 6.7 µm and NMC 622 (BA) with large particle size of 12.8 µm. Besides, reference electrodes with one type of active material as well as with two type of materials established during mixing process (BT) were manufactured. The total film thickness of all hierarchical composite electrodes were kept constant at 150 µm, while the thicknesses of TA and BA were set at 1:2, 1:1, and 2:1. Meanwhile, three kinds of thin-film cathodes with 70 µm were applied to represent the state-of-the-art approach. Subsequently, ultrafast laser ablation was applied to generate groove structures inside the electrodes. The results demonstrate that cells with thin-film or thick-film cathode only containing TA, cells with bilayer electrode containing TBA 1:2, and cells with laser-structured electrodes show higher capacity at C/2 to 5C, respectively.

Lithium‐ion batteries (LIBs) are currently the predominant energy storage power source. However, the urgent issues of enhancing electrochemical performance, prolonging lifetime, preventing thermal runaway‐caused fires, and intelligent application are obstacles to their applications. Herein, bio‐inspired electrodes owning spatiotemporal management of self‐healing, fast ion transport, fire‐extinguishing, thermoresponsive switching, recycling, and flexibility are overviewed comprehensively, showing great promising potentials in practical application due to the significantly enhanced durability and thermal safety of LIBs. Taking advantage of the self‐healing core–shell structures, binders, capsules, or liquid metal alloys, these electrodes can maintain the mechanical integrity during the lithiation–delithiation cycling. After the incorporation of fire‐extinguishing binders, current collectors, or capsules, flame retardants can be released spatiotemporally during thermal runaway to ensure safety. Thermoresponsive switching electrodes are also constructed though adding thermally responsive components, which can rapidly switch LIB off under abnormal conditions and resume their functions quickly when normal operating conditions return. Finally, the challenges of bio‐inspired electrode designs are presented to optimize the spatiotemporal management of LIBs. It is anticipated that the proposed electrodes with spatiotemporal management will not only promote industrial application, but also strengthen the fundamental research of bionics in energy storage.