Integrated Design of Nickel‐Based Coordination Compound Size Control and 3D Printing to Construct Ordered Micro‐Supercapacitors

The rapid development of micro supercapacitors requires electrode materials that possess both high redox activity and structural robustness. Nickel‐based coordination compounds are promising candidate materials, but their practical applications are hindered by the intense volume fluctuations and lattice strain during repeated redox reactions. The 1D coordination structure has inherent characteristics such as providing directional mechanical buffering and continuous charge transfer channels, which can effectively alleviate the above problems. However, the disordered arrangement of 1D structures in traditional electrode structures weakens their inherent advantages. Therefore, we successfully synthesized a series of printable 1D fibrous nickel‐based coordination compounds of different lengths using 4‐chlorosalicylate ligands that can transition from chelation dominant to carboxyl/hydroxyl bridged coordination mode. Utilizing 3D printing technology, we have fabricated NCS3@CNT@GO//MXene micro‐devices with an ordered layered structure. The specific capacitance of this device reached 381.36 mF cm −2 , and the energy density was 52.97 µWh cm −2 . Compared with the disordered NCS2@CNT@GO//MXene (273.84 mF cm −2 ) and NCS4@CNT@GO//MXene (337.44 mF cm −2 ), its specific capacitance increased by 39.2% and 13%, respectively, indicating that the ordered structure has an advantage in improving electrochemical performance. This work provides a universal approach for designing structured programmable electrodes suitable for micro energy storage.