Organic sodium-ion batteries (OSIBs) have numerous promising advantages for foreseeable large-scale applications, particularly including the convenience of performance optimization through molecular design. However, the reported organic cathodes still suffer from limited capacity, low cyclability, and poor rate performance. The tailoring of the p-conjugated system reported here can enhance the p-p intermolecular interactions, leading to insolubility, long-range layer-by-layer p-p stacking, fast-charge transport, and extraordinary stability and ionic conductivity (10 À9 cm 2 s À1 ). Consequently, the obtained cathodes delivered high electrochemical performance with high capacity ($290 mAh g À1 ), superior fast-chargedischarge ability ($160 and 100 mAh g À1 at 10 and 50 A g À1 , respectively), and ultra-long cycle life (capacity as high as 97 mAh g À1 after 10,000 cycles at 50 A g À1 ).

p-d Conjugated coordination polymers (CCPs) have attracted muchattention for various applications,although the chemical states and structures of many CCPs are still blurry. Now,aone-dimensional (1D) p-d conjugated coordination polymer for high performance sodium-ion batteries is presented. The chemical states of the obtained coordination polymer are clearly revealed. The electrochemical process undergoes at hree-electron reaction and the structure transforms from C=Nd ouble bonds and Ni II to CÀNs ingle bonds and Ni I ,r espectively.Our unintentional experiments provided visual confirmation of Ni I .T he existence of Ni I was further corroborated by its X-raya bsorption near-edge structure (XANES) and its catalytic activity in Negishi cross-coupling.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Poly(pentacenetetrone sulfide) (PPTS) as a cathode for PIBs exhibits high electrochemical performance. Novel methods are also demonstrated for inhibiting K dendrites.