Effects of Mg Doping at Different Positions in Li-Rich Mn-Based Cathode Material on Electrochemical Performance

Li-rich Mn-based layered oxides are among the most promising cathode materials for next-generation lithium-ion batteries, yet they suffer from capacity fading and voltage decay during cycling. The electrochemical performance of the material can be improved by doping with Mg. However, the effect of Mg doping at different positions (lithium or transition metals) remains unclear. Li1.2Mn0.54Ni0.13Co0.13O2 (LR) was synthesized by coprecipitation followed by a solid-state reaction. The coprecipitation stage was used to introduce Mg in TM layers (sample LR-Mg), and the solid-state reaction (st) was used to dope Mg in Li layers (LR-Mg(st)). The presence of magnesium at different positions was confirmed by XRD, XPS, and electrochemical studies. The investigations have shown that the introduction of Mg in TM layers is preferable in terms of the electrochemical performance. The sample doped with Mg at the TM positions shows better cyclability and higher discharge capacity than the undoped sample. The poor electrochemical properties of the sample doped with Mg at Li positions are due to the kinetic hindrance of oxidation of the manganese-containing species formed after activation of the Li2MnO3 component of the composite oxide. The oxide LR-Mg(st) demonstrates the lowest lithium-ion diffusion coefficient and the greatest polarization resistance compared to LR and LR-Mg.

Ce and F Dual-Doping Strategy for High Cycle Performance of Lithium-Rich Layered Oxide Materials

Li-rich layered oxides (LrLOs) attracted much attention due to their high specific capacity. However, LrLOs have disadvantages such as fast voltage decay and poor cycle stability. In this work, we propose a dual-doping strategy based on Ce and F ions to respond to the defects of LrLOs. This work shows that Ce and F have a strong synergistic effect in LrLOs cathode materials. Dual-doping makes the structure of the cathode materials more stable, which is mainly manifested by inhibiting the extraction of lattice oxygen, reducing the migration of cations during the cycle, and reducing the corrosion of the electrolyte to the cathode materials. Thereby, the work improves the cycle performance of the cathode materials. The capacity retention rate is 84.3% for 200 cycles at 1[Formula: see text]C (versus 59.6%). The median discharge voltage is 3.2155[Formula: see text]V after 200 cycles at 1[Formula: see text]C (versus 2.9485[Formula: see text]V). The voltage decay is 0.4706[Formula: see text]V for 200 cycles at 1[Formula: see text]C (versus 0.6923[Formula: see text]V). Interestingly, our research found that Ni[Formula: see text] of the Li layer also plays an important role in the process of improving cycle performance. This work provides new ideas for solving the cycle stability of LrLOs cathode materials and suppressing voltage decay.

Reaction inhomogeneity coupling with metal rearrangement triggers electrochemical degradation in lithium-rich layered cathode

High-energy density lithium-rich layered oxides are among the most promising candidates for next-generation energy storage. Unfortunately, these materials suffer from severe electrochemical degradation that includes capacity loss and voltage decay during long-term cycling. Present research efforts are primarily focused on understanding voltage decay phenomena while origins for capacity degradation have been largely ignored. Here, we thoroughly investigate causes for electrochemical performance decline with an emphasis on capacity loss in the lithium-rich layered oxides, as well as reaction pathways and kinetics. Advanced synchrotron-based X-ray two-dimensional and three-dimensional imaging techniques are combined with spectroscopic and scattering techniques to spatially visualize the reactivity at multiple length-scales on lithium- and manganese-rich layered oxides. These methods provide direct evidence for inhomogeneous manganese reactivity and ionic nickel rearrangement. Coupling deactivated manganese with nickel migration provides sluggish reaction kinetics and induces serious structural instability in the material. Our findings provide new insights and further understanding of electrochemical degradation, which serve to facilitate cathode material design improvements.

Effects of Recombination Order on Open-Circuit Voltage Decay Measurements of Organic and Perovskite Solar Cells

Non-geminate recombination, as one of the most relevant loss mechanisms in organic and perovskite solar cells, deserves special attention in research efforts to further increase device performance. It can be subdivided into first, second, and third order processes, which can be elucidated by the effects that they have on the time-dependent open-circuit voltage decay. In this study, analytical expressions for the open-circuit voltage decay exhibiting one of the aforementioned recombination mechanisms were derived. It was possible to support the analytical models with experimental examples of three different solar cells, each of them dominated either by first (PBDBT:CETIC-4F), second (PM6:Y6), or third (irradiated CH3NH3PbI3) order recombination. Furthermore, a simple approach to estimate the dominant recombination process was also introduced and tested on these examples. Moreover, limitations of the analytical models and the measurement technique itself were discussed.