LiCoO 2 is a dominant cathode material for Li-ion batteries due to its high volumetric energy density, which could potentially be further improved by charging to high voltage. Practical adoption of the high-voltage charging is, however, hindered by LiCoO 2 's structural instability at the deeply delithiated state and the associated safety concerns. Here, we achieve stable cycling of LiCoO 2 at 4.6 V (vs. Li/Li +) through trace Ti-Mg-Al co-doping. By using state-of-the-art synchrotron X-ray imaging and spectroscopic techniques, we confirm the incorporation of Mg and Al into the LiCoO 2 lattice, which inhibits the undesired phase transition at voltages above 4.5 V. On the other hand, even in trace amount, Ti segregates significantly at grain boundaries and on the surface, modifying the microstructure of the particles while stabilizing the surface oxygen at high voltage. These dopants contribute though different mechanisms and synergistically promote the cycle stability of LiCoO 2 at 4.6 V.
The thermal instability of the cathode materials in lithium‐ion batteries is an important safety issue, requiring the incorporation of several approaches to prevent thermal runaway and combustion. Systematic studies, using combined well‐defined in situ techniques, are crucial to obtaining in‐depth understanding of the structural origin of this thermal instability in overcharged cathode materials. Here time‐resolved X‐ray diffraction, X‐ray absorption, mass spectroscopy, and high‐resolution transmission electron microscopy during heating are combined to detail the structural changes in overcharged LixNi0.8Co0.15Al0.05O2 and LixNi1/3Co1/3Mn1/3O2 cathode materials. By employing these several techniques in concert, various aspects of the structural changes are investigated in these two materials at an overcharged state; these include differences in phase‐distribution after overcharge, phase nucleation and propagation during heating, the preferred atomic sites and migration paths of Ni, Co, and Mn, and their individual contributions to thermal stability, together with measuring the oxygen release that accompanies these structural changes. These results provide valuable guidance for developing new cathode materials with improved safety characteristics.
In this work, we present results from the application
of a new
in situ technique that combines time-resolved synchrotron X-ray diffraction
and mass spectroscopy. We exploit this approach to provide direct
correlation between structural changes and the evolution of gas that
occurs during the thermal decomposition of (over)charged cathode materials
used in lithium-ion batteries. Results from charged Li
x
Ni0.8Co0.15Al0.05O2 cathode materials indicate that the evolution of both
O2 and CO2 gases are strongly related to phase
transitions that occur during thermal decomposition, specifically
from the layered structure (space group R3̅m) to the disordered spinel structure (Fd3̅m), and finally to the rock-salt structure
(Fm3̅m). The state of charge
also significantly affects both the structural changes and the evolution
of oxygen as the temperature increases: the more extensive the charge,
the lower the temperature of the phase transitions and the larger
the oxygen release. Ex situ X-ray absorption spectroscopy (XAS) and
in situ transmission electron microscopy (TEM) are also utilized to
investigate the local structural and valence state changes in Ni and
Co ions, and to characterize microscopic morphology changes. The combination
of these advanced tools provides a unique approach to study fundamental
aspects of the dynamic physical and chemical changes that occur during
thermal decomposition of charged cathode materials in a systematic
way.
Lithium-rich layered oxides with the capability to realize extraordinary capacity through anodic redox as well as classical cationic redox have spurred extensive attention. However, the oxygen-involving process inevitably leads to instability of the oxygen framework and ultimately lattice oxygen release from the surface, which incurs capacity decline, voltage fading, and poor kinetics. Herein, it is identified that this predicament can be diminished by constructing a spinel Li Mn O coating, which is inherently stable in the lattice framework to prevent oxygen release of the lithium-rich layered oxides at the deep delithiated state. The controlled KMnO oxidation strategy ensures uniform and integrated encapsulation of Li Mn O with structural compatibility to the layered core. With this layer suppressing oxygen release, the related phase transformation and catalytic side reaction that preferentially start from the surface are consequently hindered, as evidenced by detailed structural evolution during Li extraction/insertion. The heterostructure cathode exhibits highly competitive energy-storage properties including capacity retention of 83.1% after 300 cycles at 0.2 C, good voltage stability, and favorable kinetics. These results highlight the essentiality of oxygen framework stability and effectiveness of this spinel Li Mn O coating strategy in stabilizing the surface of lithium-rich layered oxides against lattice oxygen escaping for designing high-performance cathode materials for high-energy-density lithium-ion batteries.
Electrochemical energy storage devices with a high energy density are an important technology in modern society, especially for electric vehicles. The most effective approach to improve the energy density of batteries is to search for high-capacity electrode materials. According to the concept of energy quality, a high-voltage battery delivers a highly useful energy, thus providing a new insight to improve energy density. Based on this concept, a novel and successful strategy to increase the energy density and energy quality by increasing the discharge voltage of cathode materials and preserving high capacity is proposed. The proposal is realized in high-capacity Li-rich cathode materials. The average discharge voltage is increased from 3.5 to 3.8 V by increasing the nickel content and applying a simple after-treatment, and the specific energy is improved from 912 to 1033 Wh kg . The current work provides an insightful universal principle for developing, designing, and screening electrode materials for high energy density and energy quality.
For LiMO 2 (M ¼ Co, Ni, Mn) cathode materials, lattice parameters, a(b), contract during charge. Here we report such changes in opposite directions for lithium molybdenum trioxide (Li 2 MoO 3 ). A 'unit cell breathing' mechanism is proposed based on crystal and electronic structural changes of transition metal oxides during charge-discharge. Metal-metal bonding is used to explain such 'abnormal' behaviour and a generalized hypothesis is developed. The expansion of the metal-metal bond becomes the controlling factor for a(b) evolution during charge, in contrast to the shrinking metal-oxygen bond as controlling factor in 'normal' materials. The cation mixing caused by migration of molybdenum ions at higher oxidation state provides the benefits of reducing the c expansion range in the early stage of charging and suppressing the structure collapse at high voltage charge. These results may open a new strategy for designing layered cathode materials for high energy density lithium-ion batteries.
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