Add time:07/19/2019         Source:sciencedirect.com

Crystalline metal-organic frameworks of divalent transition metal terephthalate belong to a new kind of high-capacity lithium storage materials. In this paper, CoCl2 aqueous solution and CoCl2·6H2O particles are comparatively used as starting materials to react with aqueous lithium terephthalate (Li2TP), resulting in the hierarchical architectures of dihydrate cobalt terephthalate (CoTP·2H2O No.1, No.2) by a solution-based π-π stacking self-assembly, respectively. Each of the two hydrated samples, as well as its well-crystallized anhydrous counterpart (CoTP No.1 or No.2), acquire a specific surface area no bigger than 4.5 m2 g−1 but deliver a reversible capacity no less than 815.0 mAh g−1 at 200 mA g−1 in the 100th cycle. The decreasing order of lithium-storage capability (CoTP·2H2O No.1 < CoTP·2H2O No.2 < CoTP No.1 < CoTP No.2) and its reverse trend of charge-transfer resistance indicate an adverse effect of crystal water, conflicting with the previously demonstrated enhancement of crystal water in inorganic cupric oxalate hydrates. Especially, combining voltage profile with its differential curve clearly reveals a 12-electron transfer lithiation-delithiation mechanism, which explains the ultrahigh reversible capacity (1234.2 mAh g−1, the 350th cycle) of CoTP No.2 structure and indicates a successful approach to the facile preparation of the organic anode material for high-performance lithium-ion batteries.

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