ABSTRACT
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.
ABSTRACT
This study evaluates the effect of equimolar substitution of manganese by cobalt or nickel in hexacyanoferrate (HCF) open frameworks as electrode materials for Na-ion batteries. As the stability of Mn-N bonds is crucial to obtain long term stability and cyclability of manganese (Mn-HCF), the samples were analyzed thoroughly using several spectroscopic and structural methods. The XPS and infrared experiments reveal that the charge density around Fe is modulated by the presence of Co or Ni, which is associated with their high polarizing power, leading to decreased cell distortion as revealed by XRD. The Rietveld refinement demonstrated that the octahedra built by 3d metals and the cyanide nitrogen were distorted with the axial bond distances being larger than the equatorial distances. This octahedral distortion promotes the spin behavior of 3/2 for Mn2+ confirmed by magnetic experiments; the arising of this spin state is attributed to d orbital splitting determined by UV-Vis experiments. Therefore, the changes upon Mn substitution are related to the modification of the covalent character of Mn-N bonds, modulated by the effect of the Ni and Co polarizing power. All these properties improve the electrochemical stability of the Ni or Co substituted materials as Na-ion batteries, leading to higher capacity retention even at higher C-rates (5C) and good capacity recovery, in comparison with those obtained for Mn-HCF.
