Addressing voltage decay in Li-rich cathodes by broadening the gap between metallic and anionic bands

Oxygen release and irreversible cation migration are the main causes of voltage fade in Li-rich transition metal oxide cathode. But their correlation is not very clear and voltage decay is still a bottleneck. Herein, we modulate the oxygen anionic redox chemistry by constructing Li2ZrO3 slabs into Li2MnO3 domain in Li1.21Ni0.28Mn0.51O2, which induces the lattice strain, tunes the chemical environment for redox-active oxygen and enlarges the gap between metallic and anionic bands. This modulation expands the region in which lattice oxygen contributes capacity by oxidation to oxygen holes and relieves the charge transfer from anionic band to antibonding metal–oxygen band under a deep delithiation. This restrains cation reduction, metal–oxygen bond fracture, and the formation of localized O2 molecule, which fundamentally inhibits lattice oxygen escape and cation migration. The modulated cathode demonstrates a low voltage decay rate (0.45 millivolt per cycle) and a long cyclic stability.

Depth-dependent valence stratification driven by oxygen redox in lithium-rich layered oxide

Lithium-rich nickel-manganese-cobalt (LirNMC) layered material is a promising cathode for lithium-ion batteries thanks to its large energy density enabled by coexisting cation and anion redox activities. It however suffers from a voltage decay upon cycling, urging for an in-depth understanding of the particle-level structure and chemical complexity. In this work, we investigate the Li1.2Ni0.13Mn0.54Co0.13O2 particles morphologically, compositionally, and chemically in three-dimensions. While the composition is generally uniform throughout the particle, the charging induces a strong depth dependency in transition metal valence. Such a valence stratification phenomenon is attributed to the nature of oxygen redox which is very likely mostly associated with Mn. The depth-dependent chemistry could be modulated by the particles’ core-multi-shell morphology, suggesting a structural-chemical interplay. These findings highlight the possibility of introducing a chemical gradient to address the oxygen-loss-induced voltage fade in LirNMC layered materials.

Dissociate lattice oxygen redox reactions from capacity and voltage drops of battery electrodes

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 Na0.6[Li0.2Mn0.8]O2 and compare it with Na2/3[Mg1/3Mn2/3]O2. Both systems display strong lattice OR activities but with distinct electrochemical stability. The comparison shows that the substantial capacity drop in Na0.6[Li0.2Mn0.8]O2 stems from non-lattice oxygen oxidations, and its voltage decay from an increasing Mn redox contribution upon cycling, contrasting those in Na2/3[Mg1/3Mn2/3]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.

An in-depth study of Sn substitution in Li-rich/Mn-rich NMC as a cathode material for Li-ion batteries

The Sn4+ substitution limit in Li1.2Ni0.13Co0.13Mn0.54−xSnxO2 is around x = 0.045. For x = 0.027 the honeycomb ordering and O3 structure is preserved. For x = 0 and x = 0.027 similar voltage fade has been obtained in the 3 V–4.55 V vs. Li/Li+ window.

Voltage fade mitigation in the cationic dominant lithium-rich NCM cathode

In the archetypal lithium-rich cathode compound Li1.2Ni0.13Co0.13Mn0.54O2, a major part of the capacity is contributed from the anionic (O2−/−) reversible redox couple and is accompanied by the transition metal ions migration with a detrimental voltage fade. A better understanding of these mutual interactions demands for a new model that helps to unfold the occurrences of voltage fade in lithium-rich system. Here we present an alternative approach, a cationic reaction dominated lithium-rich material Li1.083Ni0.333Co0.083Mn0.5O2, with reduced lithium content to modify the initial band structure, hence ~80% and ~20% of capacity are contributed by cationic and anionic redox couples, individually. A 400 cycle test with 85% capacity retention depicts the capacity loss mainly arises from the metal ions dissolution. The voltage fade usually from Mn4+/Mn3+ and/or On−/O2− reduction at around 2.5/3.0 V seen in the typical lithium-rich materials is completely eliminated in the cationic dominated cathode material.