Na-ion cathode materials operating at high voltage with a stable cycling behavior are needed to develop future high-energy Na-ion cells. However, the irreversible oxygen redox reaction at the high-voltage region in sodium layered cathode materials generates structural instability and poor capacity retention upon cycling. Here, we report a doping strategy by incorporating light-weight boron into the cathode active material lattice to decrease the irreversible oxygen oxidation at high voltages (i.e., >4.0 V vs. Na⁺/Na). The presence of covalent B–O bonds and the negative charges of the oxygen atoms ensures a robust ligand framework for the NaLi_1/9Ni_2/9Fe_2/9Mn_4/9O₂ cathode material while mitigating the excessive oxidation of oxygen for charge compensation and avoiding irreversible structural changes during cell operation. The B-doped cathode material promotes reversible transition metal redox reaction enabling a room-temperature capacity of 160.5 mAh g⁻¹ at 25 mA g⁻¹ and capacity retention of 82.8% after 200 cycles at 250 mA g⁻¹. A 71.28 mAh single-coated lab-scale Na-ion pouch cell comprising a pre-sodiated hard carbon-based anode and B-doped cathode material is also reported as proof of concept.

Solid state lithium batteries are widely accepted as promising candidates for next generation of various energy storage devices with the probability to realize improved energy density and superior safety performances. However, the interface between electrode and solid electrolyte remain a key issue that hinders practical development of solid state lithium batteries. In this review, we specifically focus on the interface between solid electrolytes and prevailing cathodes. The basic principles of interface layer formation are summarized and three kinds of interface layers can be categorized. For typical solid state lithium batteries, a most common and daunting challenge is to achieve and sustain intimate solid-solid contact. Meanwhile, different specific issues occur on various types of solid electrolytes, depending on the intrinsic properties of adjacent solid components. Our discussion mostly involves following electrolytes, including solid polymer electrolyte, inorganic solid oxide and sulfide electrolytes as well as composite electrolytes. The effective strategies to overcome the interface instabilities are also summarized. In order to clarify interfacial behaviors fundamentally, advanced characterization techniques with time, and atomic-scale resolution are required to gain more insights from different perspectives. And recent progresses achieved from advanced characterization are also reviewed here. We highlight that the cooperative characterization of diverse advanced characterization techniques is necessary to gain the final clarification of interface behavior, and stress that the combination of diverse interfacial modification strategies is required to build up decent cathode-electrolyte interface for superior solid state lithium batteries.

The oxygen redox (OR) activity is conventionally considered detrimental to the stability and kinetics of batteries. However, OR reactions are often confused by irreversible oxygen oxidation. Here, based on high-efficiency mapping of resonant inelastic x-ray scattering of both the transition metal and oxygen, we distinguish the lattice OR in Na_0.6[Li_0.2Mn_0.8]O₂ and compare it with Na_2/3[Mg_1/3Mn_2/3]O₂. Both systems display strong lattice OR activities but with distinct electrochemical stability. The comparison shows that the substantial capacity drop in Na_0.6[Li_0.2Mn_0.8]O₂ stems from non-lattice oxygen oxidations, and its voltage decay from an increasing Mn redox contribution upon cycling, contrasting those in Na_2/3[Mg_1/3Mn_2/3]O₂. We conclude that lattice OR is not the ringleader of the stability issue. Instead, irreversible oxygen oxidation and the changing cationic reactions lead to the capacity and voltage fade. We argue that lattice OR and other oxygen activities should/could be studied and treated separately to achieve viable OR-based electrodes.

Amorphous anion-rich materials would offer a previously unexplored solution for high-capacity Al-ion storage.

Realizing reversible reduction-oxidation (redox) reactions of lattice oxygen in batteries is a promising way to improve the energy and power density. However, conventional oxygen absorption spectroscopy fails to distinguish the critical oxygen chemistry in oxide-based battery electrodes. Therefore, high-efficiency full-range mapping of resonant inelastic X-ray scattering (mRIXS) has been developed as a reliable probe of oxygen redox reactions. Here, based on mRIXS results collected from a series of Li_1.17Ni_0.21Co_0.08Mn_0.54O₂ electrodes at different electrochemical states and its comparison with peroxides, we provide a comprehensive analysis of five components observed in the mRIXS results. While all the five components evolve upon electrochemical cycling, only two of them correspond to the critical states associated with oxygen redox reactions. One is a specific feature at 531.0 eV excitation and 523.7 eV emission energy, the other is a low-energy loss feature. We show that both features evolve with electrochemical cycling of Li_1.17Ni_0.21Co_0.08Mn_0.54O₂ electrodes, and could be used for characterizing oxidized oxygen states in the lattice of battery electrodes. This work provides an important benchmark for a complete assignment of all mRIXS features collected from battery materials, which sets a general foundation for future studies in characterization, analysis, and theoretical calculation for probing and understanding oxygen redox reactions.