Branded with low cost and a high degree of safety, with an ambitious aim of substituting lithium-ion batteries in many fields, sodium-ion batteries have received fervid attention in recent years after being dormant for decades. Layered materials are a major focus of study owing to the extensive experience already gained in lithium-ion batteries, and the pursuit of a Mn-rich composition is critical to reduce the cost while retaining the performance. This review provides a timely update of the recent progress of Mn-rich layered materials for sodium-ion batteries based on the understandings of the phase forming principles, structure transformation upon cycling and charge compensation mechanisms and discusses potential ambiguities in the pursuit of high-performance materials.
Pre-extracting
Li+ from Li-rich layered oxides by chemical
method is considered to be a targeted strategy for improving this
class of cathode material. Understanding the structural evolution
of the delithiated material is very important because this is directly
related to the preparation of electrochemical performance enhanced
Li-rich material. Herein, we perform a high temperature reheat treatment
on the quantitatively delithiated Li-rich materials with different
amounts of surface defect-spinel phase and carefully investigate the
structural evolution of these delithiated materials. It is found that
the high temperature reheat treatment could cause the decomposition
of the unstable surface defect-spinel structure, followed by the rearrangement
of transition metal ions to form the thermodynamically stable phases,
More importantly, we find that this process has high correlation with
the remaining Li-content in the delithiated material. When the amount
of extracted Li+ is relatively small (corresponding to
the higher remaining Li-content), the surface defect-spinel phase
could be dominantly decomposed into the LiMO2 (M = Ni,
Co, and Mn) layered phase along with the significant improvement of
electrochemical performance, and continuing to decrease remaining
Li-content could lead to the emergence of M3O4-type spinel impurity embedding in the final product. However, when
the extracted Li+ further achieves a certain amount, after
the high temperature heat-treatment the Mn-rich Li2MnO3 phase (C2/m) could be separated
from Ni-rich phases (including R
m, Fd
m, and Fm
m), thus resulting in a sharp deterioration of initial capacity
and voltage. These findings suggest that reheating the delithiated
Li-rich material to high temperature may be a simple and effective
way to improve the predelithiation modification method, but first
the amount of extracted Li+ should be carefully optimized
during the delithiation process.
Multivalent transition metal oxides possess abundant phase and valence states, the transition of which is closely related to a wide range of functionalities that have applications in various areas, such as rechargeable batteries, supercapacitors,
Lithium-rich and manganese-based oxides (LRMO) with anionic redox behavior are regarded as the cathode material for the next generation commercial lithium-ion batteries (LIBs) that are most likely to achieve the...
Lithium‐rich and manganese‐based oxide (LRMO) cathode materials are regarded as promising cathode materials for lithium‐ion batteries with anionic redox characteristics and higher specific energy density. However, the complex initial structure and complicated reaction mechanism of LRMO is controversial. Herein, the reaction mechanism and unusual electrochemical phenomena are reconsidered after proposing the concept of structure distribution between Li2MnO3 and LiMO2 structures. The initial structure states show different types of composition characteristics of Li2MnO3 and LiMO2, including “large and isolated distribution” and “uniformly dispersed distribution” characteristics, as summarized by multiple aberration correction scanning transmission electron microscopy observations at the atomic‐scale for cross sectional samples. Based on the density functional theory calculations, X‐ray absorption spectroscopy, and atomic‐scale observations during the different voltage states, the results accordingly suggest that the distribution characteristic is the essential cause of the unusual behavior in LRMO. It governs the reaction behavior, leading to the changes in electronic structure of O2p and TM3d, and the maintenance of layered structure, reversibility of the anionic redox, as well as, the voltage hysteresis. This work constructs the interrelationships of electrochemical behavior—distribution characteristic—reaction mechanism, contributing to the further application of LRMO materials in the electric vehicle market.
Benefiting from the advanced solid-state electrolytes
(SSEs), conventional
cathodes have been widely applied in all-solid-state lithium batteries
(ASSLBs). However, Li-rich Mn-based (LRM) cathodes, which possess
enhanced discharge capacities beyond 250 mA h g–1, have not yet been studied in ASSLBs. In this work, the practical
application of LRM cathodes in ASSLBs using a high-voltage-stability
halide SSE (Li3InCl6, LIC) is reported for the
first time. Furthermore, we decipher that the active oxygen released
from LRM cathodes at a high operation voltage seriously oxidizes the
LIC electrolytes, thus resulting in the large interfacial resistance
between cathodes and electrolytes and hindering their industrialized
application in ASSLBs. Therefore, surface chemistry engineering of
LRM cathodes with an ionic conductive coating material of LiNbO3 (LNO) is employed to stabilize the LRM/LIC interface. Consequently,
the LRM-based ASSLBs deliver a high specific capacity of 221 mA h
g–1 at 0.1 C and a decent cycle life of 100 cycles.
This contribution gives insights into studying the interfacial issues
between LRM cathodes and halide electrolytes and sheds light on the
application of LRM cathode materials in ASSLBs.
Lithium‐rich layered oxides (LLOs) are promising candidate cathode materials for safe and inexpensive high‐energy‐density Li‐ion batteries. However, oxygen dimers are formed from the cathode material through oxygen redox activity, which can result in morphological changes and structural transitions that cause performance deterioration and safety concerns. Herein, a flake‐like LLO is prepared and aberration‐corrected scanning transmission electron microscopy (STEM), in situ high‐temperature X‐ray diffraction (HT‐XRD), and soft X‐ray absorption spectrum (sXAS) are used to explore its crystal facet degradation behavior in terms of both thermal and electrochemical processes. Void‐induced degradation behavior of LLO in different facet reveals significant anisotropy at high voltage. Particle degradation originates from side facets, such as the (010) facet, while the close (003) facet is stable. These results are further understood through ab initio molecular dynamics calculations, which show that oxygen atoms are lost from the {010} facets. Therefore, the facet degradation process is that oxygen molecular formed in the interlayer and accumulated in the ab plane during heating, which result in crevice‐voids in the ab plane facets. The study reveals important aspects of the mechanism responsible for oxygen ‐anionic activity‐based degradation of LLO cathode materials used in lithium‐ion batteries. In particular, this study provides insight that enables precise and efficient measures to be taken to improve the thermal and electrochemical stability of an LLO.
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