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Cation doping is one of the most dynamic strategies to enhance the electrochemical properties of cathode materials for lithium-ion batteries. Nevertheless, the maximum partial substitution capacity depends on the solubility of each metal ion, and so the formation of impurities is a very common consequence. Thus, the correlation between electrochemical performance and the doping effect is frequently unknown. In this study, the effect of the partial substitution of copper by manganese, iron or nickel in Li2CuO2 is evaluated, as well as the effect on the electrochemical performance of the modified Li2CuO2 samples as lithium ion battery cathode materials. XRD characterization confirmed single phase formation for all samples, and the incorporation of the transition metal in the Li2CuO2 structure was evaluated by XRD profile fitting, EPR and 7Li-NMR. The results showed modifications in intra- and inter-chain interactions, associated with the variations in the Cu–O–Cu bond angle and changes in magnetic order, due to the presence of the doping transition metal. Among all samples, only manganese partial substitution reveals a drastic improvement in the electrochemical stability during the charge/discharge processes even at potentials higher than 3.9 V. It was corroborated that the higher stability is attributed to (i) the increase in the superexchange interactions between the copper sites and manganese, directly modifying lithium diffusivity and electronic conductivity, both inferred from dynamic thermogravimetric analysis for CO2 sorption and conductivity tests, respectively and (ii) the lower propensity to enable O2 evolution during several charge cycles. These results are totally attributed to manganese cation partial substitution, which has a huge impact on the utilization of copper-based materials in real applications.

Two novel semiconducting coordination oligomers with 1D chain structures, namely [H0.07 CuI0.65CuII0.14(μ-p-CNC6H4CO2)·0.9H2O]n and [Ag(μ-p-CNC6H4CO2)]n, were obtained and characterized by XRD powder patterns, and XPS, EPR, UV-vis-NIR, IR and Raman spectroscopy. According to XRD analysis, CuICuII–ICNBA is an amorphous solid, while AgI–ICNBA crystalizes with a monoclinic unit cell in the C2/c space group (Z = 4). The composition and further information of CuICuII–ICNBA were obtained from the spectroscopic data. In correspondence with the quantification of terminal groups from high-resolution XPS spectra, CuICuII–ICNBA and AgI–ICNBA are composed of an average of 9 and 7 monomer units, respectively, resulting in 1D-oligomers. The spectroscopic evidence indicates that CuICuII–ICNBA is better described as a non-stoichiometric coordination oligomer (where non-integer ratios of metal ions can be accommodated), while AgI–ICNBA is stoichiometric. In both materials, each metal center is linked by two μ-η1:η1-p-isocyanobenzoate ligands forming microfibers of around 120 nm (CuICuII-material) and 310 nm (AgI-material) in average diameters with optical band gaps of 2.60 eV and 2.17 eV, respectively.