Improved Na+ adsorption performance and storage mechanism of cobalt hexacyanoferrate/polyaniline composite during the hybrid capacitive deionization process

[Display omitted] •The CoHCF/PANI composite with regular structure was finely customized.•The synergistic redox reactions of CoHCF and PANI layers improve HCDI performance.•The CoHCF/PANI electrode is more suitable as the negative electrode. In order to realize high desalting capacity of capacitive deionization (CDI) system, cobalt hexacyanoferrate/polyaniline (CoHCF/PANI) composite with hollow hierarchical tubular structure was finely prepared by employing conductive hollow PANI tube as the interconnection skeleton for CoHCF cubic particles grown in situ, thereby endowing this composite with good conductivity, abundant redox active sites and stable structure. The synergistic effect between the CoHCF layer and PANI layer makes the CoHCF/PANI electrode possess superior specific capacitance (263.8F·g−1) and high contribution of the capacitance behavior (87.8 %) at 5 mV·s−1. Compared with either the single PANI or CoHCF electrode, the CoHCF/PANI electrode exhibits outstanding salt adsorption capacity (30.48 mg·g−1), rapid salt adsorption rate (3.66 mg·g−1·min−1) and excellent cycle stability (retention rate 98.1 %). Different from the CoHCF/PANI(+)‖AC(−) cell, there is no inversion peak in the AC(+)‖CoHCF/PANI(−) cell, which testifies that the CoHCF/PANI electrode is easier to capture Na+ ions. Based on the XPS spectra before and after desalination tests, the Na+ adsorption mechanism of the CoHCF/PANI electrode as cathode for the hybrid capacitive deionization (HCDI) system was further explored. It is found that the change of element valence in CoHCF/PANI composites (reduction of Fe3+ to Fe2+ and Co3+ to Co2+ in CoHCF, partial reduction of −C = N+ to −N–H- in PANI) is the main factor leading to Na+ intercalation. This study emphasizes the significance for fine design of the electrode material and strategic configuration of the HCDI cell.