Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li_1.17–x Ni_0.21Co_0.08Mn_0.54O₂, these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by > 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.

Stable dispersion of reduced graphene in various organic solvents was achieved via noncovalent functionalization with amine-terminated polymers. An aqueous dispersion of reduced graphene was prepared by chemical reduction of graphene oxide in aqueous media and was vacuum filtered to generate reduced graphene sheets. Good solvents and nonsolvents for the dried reduced graphene were evaluated using a solubility test. To achieve stable dispersion in the evaluated nonsolvents, amine-terminated polystyrene was noncovalently functionalized to the graphene, while graphene sheets were phase transferred via sonication from aqueous phase to the organic nonsolvent phase, including the amine-terminated polymers. Thorough FTIR and Raman spectroscopy investigation verified that the protonated amine terminal group of polystyrene underwent noncovalent functionalization to the carboxylate groups at the graphene surface, providing the high dispersibility in various organic media.

The insertion of guest species in graphite is the key feature utilized in applications ranging from energy storage and liquid purification to the synthesis of graphene. Recently, it was discovered that solvated-Na-ion intercalation can occur in graphite even though the insertion of Na ions alone is thermodynamically impossible; this phenomenon enables graphite to function as a promising anode for Na-ion batteries. In an effort to understand this unusual behavior, we investigate the solvated-Na-ion intercalation mechanism using in operando X-ray diffraction analysis, electrochemical titration, real-time optical observation, and density functional theory (DFT) calculations. The ultrafast intercalation is demonstrated in real time using millimeter-sized highly ordered pyrolytic graphite, in which instantaneous insertion of solvated-Na-ions occurs (in less than 2 s). The formation of various stagings with solvated-Na-ions in graphite is observed and precisely quantified for the first time. The atomistic configuration of the solvated-Na-ions in graphite is proposed based on the experimental results and DFT calculations. The correlation between the properties of various solvents and the Na ion co-intercalation further suggests a strategy to tune the electrochemical performance of graphite electrodes in Na rechargeable batteries.