Layered Oxide Cathode Materials Research Articles

Operando Electrochemical Fluorescent Microscopy to Predict Li-Ion Battery Performance

A real-time, high-throughput visualization technique for heterogeneity in lithium-ion battery (LIB) electrodes is necessary to understand battery performance on a mechanistic level. Our group, along with others, has seen that battery performance is governed by short range (<20 um) electron transfer between the active material and carbon binder domain (CBD) in electrodes [1]–[3]. Available imaging techniques for visualizing the electronic connectivity of LIB electrodes are limited to nanoscale, single particle resolutions using sophisticated synchrotron X-ray or electron microscopy [4]–[6]. Optical microscopy offers the correct spatial resolution for visualizing the submicron connections of active particles to CBD, but is limited by the colorimetry of electrode materials- with graphite being the exception due to its visible color change during lithiation [7]. There is a rapidly growing body of research interested in studying the ionic diffusion pathways of Li-ion using operando optical microscopy, however none currently exist for studying the submicron electronic connectivity using an operando approach- especially under a industrially applicable lens [8]. To the best of our knowledge, this study presents the first spatially- and time- resolved technique for visualizing the electronic connectivity of commercial LIB electrodes using operando electrochemical fluorescent microscopy (EFM). This technique relies on the principle of electrofluorochromism, which we use to our advantage for a simple electrochemical system involving heterogeneous electron transfer. This allows us to use fluorescence as a real-time tracker for electronic heterogeneity, where electronic ‘dead-zones’ present as non-fluorescent regions in 2D images.Using this technique, we visualize commonly used commercial LIB electrodes (carbon content 1-4%, regimented processing), including NMC (LiNixMnyCo1-x-yO2), LFP (LiFePO4), and LCO (LiCoO2) against formulaically similar in-house made LIB electrodes (< 3.5% carbon content) as a proof of concept. We first validate the efficacy of this technique by testing commercial NMC, with a flaked off piece of active material, to show that areas of electronic discontinuities can in fact be represented by non-fluorescence (Fig.1.) We also find that when compared to commercial electrodes, those which are fabricated in house reveal isolated active particles, agglomerated carbon islands, and dead zones, undiscernible by brightfield imaging (Fig. 2.) Global feature extraction is performed on post-processed images to quantify electrode topology and evaluate electronic connectivity of active particles of battery electrodes, as well as heterogeneous mapping to determine the heterogeneity index of electrodes imaged. Testing our technique on low- and high- performing electrodes from an established library of coin-cell data allows for a straightforward way of correlating performance metrics to heterogeneity features. This quick (<1hr), reproducible visualization technique is general enough to be used to study the electronic connectivity of emerging new battery electrodes, as well as verify commercially available ones. Using this approach to verify LIB electrodes prior to assembly could save months to years of battery testing by being used as an alternative to lengthy full cell testing.[1] S. L. Morelly, N. J. Alvarez, and M. H. Tang, “Short-range contacts govern the performance of industry-relevant battery cathodes,” Journal of Power Sources, vol. 387, pp. 49–56, May 2018, doi: 10.1016/j.jpowsour.2018.03.039.[2] R. M. Saraka, S. L. Morelly, M. H. Tang, and N. J. Alvarez, “Correlating Processing Conditions to Short- and Long-Range Order in Coating and Drying Lithium-Ion Batteries,” ACS Appl. Energy Mater., vol. 3, no. 12, pp. 11681–11689, Dec. 2020, doi: 10.1021/acsaem.0c01305.[3] J. Entwistle, R. Ge, K. Pardikar, R. Smith, and D. Cumming, “Carbon binder domain networks and electrical conductivity in lithium-ion battery electrodes: A critical review,” Renewable and Sustainable Energy Reviews, vol. 166, p. 112624, Sep. 2022, doi: 10.1016/j.rser.2022.112624.[4] S. Li et al., “Mutual modulation between surface chemistry and bulk microstructure within secondary particles of nickel-rich layered oxides,” Nat Commun, vol. 11, no. 1, Art. no. 1, Sep. 2020, doi: 10.1038/s41467-020-18278-y.[5] P.-C. Tsai et al., “Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries,” Energy Environ. Sci., vol. 11, no. 4, pp. 860–871, Apr. 2018, doi: 10.1039/C8EE00001H.[6] A. Singer et al., “Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging,” Nat Energy, vol. 3, no. 8, Art. no. 8, Aug. 2018, doi: 10.1038/s41560-018-0184-2.[7] Y. Yamagishi, H. Morita, Y. Nomura, and E. Igaki, “Visualizing Lithiation of Graphite Composite Anodes in All-Solid-State Batteries Using Operando Time-of-Flight Secondary Ion Mass Spectrometry,” J. Phys. Chem. Lett., vol. 12, no. 19, pp. 4623–4627, May 2021, doi: 10.1021/acs.jpclett.1c01089.[8] A. J. Merryweather, C. Schnedermann, Q. Jacquet, C. P. Grey, and A. Rao, “Operando optical tracking of single-particle ion dynamics in batteries,” Nature, vol. 594, no. 7864, Art. no. 7864, Jun. 2021, doi: 10.1038/s41586-021-03584-2. Figure 1

First-Principle Insight of Synergistic Modification Mechanism in P2-Type Layered Oxide Cathode Material with Anionic Redox Activity for Sodium-Ion Batteries

Layered oxides exhibiting anionic redox activity have gained attention as a promising material in both Na-ion batteries owing to their additional capacity provided through oxygen redox chemistry. However, unfavorable side effects such as irreversible phase transformation, hysteresis, and gas evolution, usually arise during the stabilization process of the unstable electron holes generated by the redox reaction of oxygen. To address these challenges, we co-dope Cu and Ca in the pristine Nax[Mg0.28Mn0.72]O2 (NMMO) and propose the P2-type NaxCa0.03Mg0.22Cu0.11Mn0.67O2 (NCaMCMO) Na-deficient cathode material which demonstrates high specific capacity with minimal phase change. In this work, we employed the density functional theory (DFT) calculations to investigate the underlying mechanisms of the synergistic modification strategy in both transition metal and alkali metal layers. The substitution of electrochemically active Cu induced variations in the electronic structure near the Fermi level, indicating an inherent change in redox chemistry. The computational results of the local structure provide a deeper understanding of the oxygen-stabilizing effect of Cu. Furthermore, we analyze the nature of the Ca insertion as a pillar in an alkali-metal layer, which mitigates phase transformation to the kinetically unfavorable O2 phase through phase energy comparison. The calculations manifest that Ca doping effectively extends the P2 phase into a deeper charging state. This work elucidates fundamental mechanisms for enhancing cathode materials in future battery design.

A New High-Valent Fe Redox Couple in Intercalation Electrodes

The overwhelming majority of layered oxide cathode materials are based on the redox activity of expensive and scarce transition metals like Co and Ni. While the Fe-redox based material LiFePO4 has become increasingly attractive due to its low cost, its low gravimetric energy density and relatively low operating voltage limit its use cases. A high-voltage Fe-based layered oxide cathode would provide high energy density utilizing the redox-activity of the most abundant transition metal in Earth’s crust, but such a material that provides stable and reversible electrochemical performance remains elusive. Indeed, high-voltage Fe-redox in oxides is plagued by cation disorder and oxygen dimerization, which leads to capacity fading and large voltage hysteresis (> 1 V).[1]In contrast, the layered oxide cathode Li4FeSbO6 (equivalently, Li[Li1/3Fe1/3Sb1/3]O2, abbreviated LFSO) exhibits <0.2 V of hysteresis, and a discharge plateau at 4.2 V versus Li/Li+ with two-electron capacity.[2] Both the exceptional electrochemical reversibility of this material and its phase separating nature upon (de)intercalation raise questions about the origin of these properties that are unusual for layered Fe oxide cathodes. In this work, we will discuss our efforts to probe the electronic structure of LFSO with Fe L–edge x–ray absorption (XAS) and 57Fe Mössbauer spectroscopy, as well as O K–edge resonant inelastic x–ray scattering spectroscopy (RIXS). The combination of these element-specific and valence-state sensitive techniques, in conjunction with charge-transfer multiplet and density functional theory calculations, allows us to reveal the electronic structure changes at Fe and O as a function of state of charge for the first time. Correlating these electronic structure changes with synchrotron diffraction measurements, we reveal a unique redox compensation mechanism that readily rationalizes the exceptional electrochemical reversibility, unlocking a new direction for high-voltage, Fe-based redox systems.

A High-Entropy Intergrowth Layered-Oxide Cathode with Enhanced Stability for Sodium-Ion Batteries.

Layered transition metal oxides are widely considered as ideal cathode materials for SIBs. However, the existing P2 and O3 structures possess specific issues, which limit their practical applications. To address these issues, this work designed a novel intergrowth layered oxide cathode with P2 and O3 phases by implementing Cu and Ti into the structure with the formation of high-entropy cathode materials with superior performance for SIBs. The electrochemical test results show that the optimized high-entropy cathode with the P2/O3 intergrowth structure possesses a high initial discharge capacity of 157.85 mAh g-1 at 0.1 C, an excellent rate performance of 84.41 mAh g-1 at 10 C, and long-term stability with capacity retention of 83.25 % after 500 cycles at 5 C. Furthermore, the analysis results of ex situ XRD and in situ XRD indicate that the adverse phase transition of P2-O2 under high voltage is effectively suppressed. This work indicates that the integration of high-entropy strategy with the two-phase intergrowth structure can effectively stabilize the layered structure, suppress the slipping of transition metal layers, and improve electrochemical performance, which provides a new approach for designing high-performance and practical layered transition metal oxide cathode materials for advanced SIBs.

Enhancing electrochemical performance of sodium-ion batteries: Optimal Ca2+ doping in O3-NaNi0.33Mn0.33Fe0.33O2 layered oxide cathode materials

Current sodium-ion battery technologies are hindered by limitations in cathode material performance, including insufficient cycle stability and low energy density, which impede their wider application and competitiveness with lithium-ion counterparts. Addressing these challenges requires innovative material engineering to improve electrochemical properties and operational durability. In this study, we synthesized a series of Na1-2xCax(Ni0.33Mn0.33Fe0.33)O2 (x = 0, 0.015, 0.025, 0.04, 0.05), by doping with electrochemically inactive Ca2+. Our findings demonstrate that doping with Ca2+ significantly enhances the electrochemical performance, as evidenced by comparisons with undoped materials. Specifically, the material Na0.95Ca0.025(Ni0.33Mn0.33Fe0.33)O2, synthesized at 900 °C, showed the best electrochemical performance, achieving an initial discharge specific capacity of 137 mAh/g within a voltage range of 2–4 V, maintaining a capacity of 117 mAh/g at a 5C discharge rate, and exhibiting a capacity retention rate of 96.2 % after 50 cycles at 1C. Additionally, Ca2+ doping was found to enhance the air stability, with negligible change in initial discharge capacity after exposure to air for 24 and 72 h. This doping strategy not only improves the performance of sodium-ion batteries but also supports the development of high-energy–density industrial batteries, offering a viable approach to designing other layered oxide materials.

A Unique Wide‐Spacing Fence‐Type Superstructure for Robust High‐Voltage O3‐Type Sodium Layered Cathode

AbstractEnhancing the energy density of layered oxide cathode materials is of great significance for realizing high‐performance sodium‐ion batteries and promoting their commercial application. Lattice oxygen redox at high voltage usually enables a high capacity and energy density. But the structural degradation, severe voltage decay, and the resultant poor cycling performance caused by irreversible oxygen release seriously restrict the practical application. Herein we introduce a novel fence‐type superstructure (2a×3a type supercell) into O3‐type layered cathode material Na0.9Li0.1Ni0.3Mn0.3Ti0.3O2 and achieve a stable cycling performance at a high voltage of 4.4 V. The fence‐type superstructure effectively inhibits the formation of the vacancy clusters resulting from out‐of‐plane Li migration and in‐plane transition metal migration at high voltage due to the wide d‐spacing, thereby significantly reducing the irreversible release of lattice oxygen and greatly stabilizing the crystal structure. The cathode exhibits a high energy density of 545 Wh kg−1, a high rate capability (112.8 mAh g−1 at 5 C) and a high cycling stability (85.8 %@200 cycles with a high initial capacity of 148.6 mAh g−1 at 1 C) accompanied by negligible voltage attenuation (98.5 %@200 cycles). This strategy provides a distinct spacing effect of superstructure to design stable high‐voltage layered cathode materials for Na‐ion batteries.

A Unique Wide-Spacing Fence-Type Superstructure for Robust High-Voltage O3-Type Sodium Layered Cathode.

Enhancing the energy density of layered oxide cathode materials is of great significance for realizing high-performance sodium-ion batteries and promoting their commercial application. Lattice oxygen redox at high voltage usually enables a high capacity and energy density. But the structural degradation, severe voltage decay, and the resultant poor cycling performance caused by irreversible oxygen release seriously restrict the practical application. Herein we introduce a novel fence-type superstructure (2a×3a type supercell) into O3-type layered cathode material Na0.9Li0.1Ni0.3Mn0.3Ti0.3O2 and achieve a stable cycling performance at a high voltage of 4.4 V. The fence-type superstructure effectively inhibits the formation of the vacancy clusters resulting from out-of-plane Li migration and in-plane transition metal migration at high voltage due to the wide d-spacing, thereby significantly reducing the irreversible release of lattice oxygen and greatly stabilizing the crystal structure. The cathode exhibits a high energy density of 545 Wh kg-1, a high rate capability (112.8 mAh g-1 at 5 C) and a high cycling stability (85.8 %@200 cycles with a high initial capacity of 148.6 mAh g-1 at 1 C) accompanied by negligible voltage attenuation (98.5 %@200 cycles). This strategy provides a distinct spacing effect of superstructure to design stable high-voltage layered cathode materials for Na-ion batteries.

Unveiling the role of fluorinated interface on anionic redox chemistry in Li-rich layered oxide cathode materials towards high-energy Li metal batteries

The utilization of Lithium-rich materials (LR) with oxygen anionic redox (OAR) activity as cathode materials in Li metal batteries has gradually emerged as a prevailing trend in designing high-specific energy batteries. However, the interface design of LR and its influence mechanism on anionic redox chemistry are still ambiguous. Herein, in-situ interface engineering with an LiF-rich cathode-electrolyte interface (CEI) using all-fluorinated electrolyte was proposed and the role of the CEI on OAR was clarified. The shielding effect on high-valence oxygen ions is revealed that the dense, uniform, thin, and robust LiF-rich CEI protects high-valence oxygen ions from the electrolyte, inhibits electrolyte decomposition and interface thickening, and ameliorates structural degradation and oxygen loss of LR. And a more critical effect of CEI on the OAR process is demonstrated that the LiF-rich CEI layer prevents molecular oxygen in the bulk from escaping into the electrolyte as O2 gas and makes the oxidized oxygen exists more in the form of peroxo-like oxygen dimer O2n−. Besides the stabilization of OAR in the cathode side, the all-fluorinated electrolyte along with its enhancement in the Li anode enable high safety, excellent cycling stability, and fast charging performance for high energy lithium metal batteries.

Study on the role of d electronic donor in Ni-rich layered oxide cathode materials for Li-ion battery

The further development of electrochemical devices and electric vehicles requires advanced Li-ion battery with higher energy density and longer lifetimes. Ni-rich LiNi0.8Co0.1Mn0.1O2 layered oxide cathodes are receiving increased attention due to its high specific capacity. Nevertheless, the role of d electrons in Ni-rich cathodes has not been uniformly reported, which hinders the design of high-performance Ni-rich cathodes. To address this issue, the role of d electronic donor in Ni-rich layered oxide cathode materials was investigated by first principles calculations and explored the mechanism for enhancing the electrochemical performance in this work. The results show that the d electronic donor V and Mo can elevate the intercalation potential, improve the stability, and enhance the diffusion rate of Li-ions in Ni-rich cathode. This theoretical study complements the mechanism for improving the electrochemical performance of Ni-rich cathode, and provides a theoretical basis for the design of high-performance Li-ion battery.

Origins of High Air Sensitivity and Treatment Strategies in O3-Type NaMn1/3 Fe1/3Ni1/3O2.

Sodium-ion layered oxides are one of the most highly regarded sodium-ion cathode materials and are expected to be used in electric vehicles and large-scale grid-level energy storage systems. However, highly air-sensitive issues limit sodium-ion layered oxide cathode materials to maximize cost advantages. Industrial and scientific researchers have been developing cost-effective air sensitivity treatment strategies with little success because the impurity formation mechanism is still unclear. Using density functional theory calculations and ab initio molecular dynamics simulations, this work shows that the poor air stability of O3-type NaMn1/3Fe1/3Ni1/3O2 (NMFNO) may be as follows: (1) low percentage of nonreactive (003) surface; (2) strong surface adsorption capacity and high surface reactivity; and (3) instability of the surface sodium ions. Our physical images point out that the high reactivity of the NMFNO surface originates from the increase in electron loss and unpaired electrons (magnetic moments) of the surface oxygen active site as well as the enhanced metal coactivation effect due to the large radius of the sodium ion. We also found that the hydrolysis reaction requires a higher reactivity of the surface oxygen active site, while the carbon hybridization mode transformation in carbonate formation depends mainly on metal activation and does not even require the involvement of surface oxygen active sites. Based on the calculation results and our proposed physical images, we discuss the feasibility of these treatment strategies (including surface morphology modulation, cation/anion substitution, and surface configuration design) for air-sensitive issues.

Decoding Li+/H+ ion exchange route toward low-temperature synthesis of layered oxide cathode materials for lithium-ion batteries

Decoding Li+/H+ ion exchange route toward low-temperature synthesis of layered oxide cathode materials for lithium-ion batteries

Upcycling degraded layered oxide cathodes from spent lithium-ion batteries toward emerging materials: A review

The increasing volume of spent lithium-ion batteries (LIBs) induces severe environmental pollution besides a waste of resources, therefore underscoring an ever-pressing need for effective recycling protocols. Layered oxide cathode materials, which are the most important and valuable component in these spent LIBs, should be prioritized for proper treatment. Currently, the conventional hydrometallurgical and pyrometallurgical recycling methodologies are being supplanted by the non-destructive direct regeneration approaches, which can minimize both waste production and energy consumption. Moreover, the technology of upcycling, which is committed to transform the degraded layered oxide cathodes into emerging functional materials, is burgeoning as another dimension to this paradigm shift. This paper briefly summarizes the degradation mechanisms of layered oxide materials during their cycling and the current treatments of these degraded materials; particularly, the main content focuses on the recent breakthroughs in upcycling strategies for these degraded materials. Looking to the future, the upcycling technology may lead to a final solution for eco-friendly, close-looped, and sustainable utilization of degraded battery materials.

Unraveling Mechanism for Microstructure Engineering toward High-Capacity Nickel-Rich Cathode Materials.

Microstructural engineering on nickel-rich layered oxide (NRLO) cathode materials is considered a promising approach to increase both the capacity and lifespan of lithium-ion batteries by introducing high valence-state elements. However, rational regulation on NRLO microstructures based on a deep understanding of its capacity enhancement mechanism remains challenging. Herein for the first time, it is demonstrated that an increase of 14mAhg-1 in reversible capacity at the first cycle can be achieved via tailoring the micro and nano structure of NRLO through introducing tungsten. Aberration-corrected scanning transmission electron microscopy (STEM) characterization reveals that the formation of a modified microstructure featured as coherent spinel twin boundaries. Theoretical modeling and electrochemical investigations further demonstrate that the capacity increase mechanism is related to such coherent spinel twin boundaries, which can lower the Li+ diffusion barrier and thus allow more Li+ to participate in deeper phase transitions. Meanwhile, the surface and grain boundaries of NRLOs are found to be modified by generating a dense and uniform LiWxOy phase, which further extends its cycle life by reducing side reactions with electrolytes. This work enables a comprehensive understanding of the capacity-increased mechanism and endows the remarkable potential of microstructural engineering for capacity- and lifespan-increased NRLOs.

Surface Gradient Ni-Rich Cathode for Li-Ion Batteries.

Nickel-rich layered oxide cathode material LiNixCoyMnzO2 (NCM) has emerged as a promising candidate for next-generation lithium-ion batteries (LIBs). These cathode materials possess high theoretical specific capacity, fast electron/ion transfer rate, and high output voltage. However, their potential is impeded by interface instability, irreversible phase transition, and the resultant significant capacity loss, limiting their practical application in LIBs. In this work, a simple and scalable approach is proposed to prepare gradient cathode material (M-NCM) with excellent structural stability and rate performance. Taking advantage of the strong coordination of Ni2+ with ammonia and the reduction reaction of KMnO4, the elemental compositions of the Ni-rich cathode are reasonably adjusted. The resulted gradient compositional design plays a crucial role in stabilizing the crystal structure, which effectively mitigates Li/Ni mixing and suppresses unwanted surficial parasitic reactions. As a result, the M-NCM cathode maintains 98.6% capacity after 200 cycles, and a rapid charging ability of 107.5 mAh g-1 at 15 C. Furthermore, a 1.2 Ah pouch cell configurated with graphite anode demonstrates a lifespan of over 500 cycles with only 8% capacity loss. This work provides a simple and scalable approach for the in situ construction of gradient cathode materials via cooperative coordination and deposition reactions.

An Active Strategy to Reduce Residual Alkali for High-Performance Layered Oxide Cathode Materials of Sodium-Ion Batteries.

Residual alkali is one of the biggest challenges for the commercialization of sodium-based layered transition metal oxide cathode materials since it can even inevitably appear during the production process. Herein, taking O3-type Na0.9Ni0.25Mn0.4Fe0.2Mg0.1Ti0.05O2 as an example, an active strategy is proposed to reduce residual alkali by slowing the cooling rate, which can be achieved in one-step preparation method. It is suggested that slow cooling can significantly enhance the internal uniformity of the material, facilitating the reintegration of Na+ into the bulk material during the calcination cooling phase, therefore substantially reducing residual alkali. The strategy can remarkably suppress the slurry gelation and gas evolution and enhance the structural stability. Compared to naturally cooled cathode materials, the capacity retention of the slowly cooled electrode material increases from 76.2% to 85.7% after 300 cycles at 1C. This work offers a versatile approach to the development of advanced cathode materials toward practical applications.

One-Step Realization of Layered/Spinel Heterostructures and Na Doping by Sodium Dodecyl Sulfate-Assisted Sol-Gel Method for Li-Ion Batteries.

Li-rich layered oxide cathodes have attracted extensive attention due to their high energy density. However, due to the low initial Coulombic efficiency and the capacity fading and voltage fading during cycling, its practical application is still a great challenge. Here, we report the one-step realization of layered/spinel heterostructures and Na doping by the sodium dodecyl sulfate (SDS)-assisted sol-gel method. The spinel phase provides 3D diffusion channels for Li-ions, and sodium doping changes the layered lattice constant and expands the layer spacing. Therefore, the designed Li1.15Mn0.54Ni0.13Co0.13Na0.05O2 (SDS-2) cathode possesses excellent electrochemical performance such as higher initial Coulombic efficiency and rate capacity and also alleviates voltage decay. The initial discharge-specific capacity of SDS-2 is 298.8 mAh g-1 at 0.1 C, and the discharge-specific capacity can reach 111.7 mAh g-1 at 10 C. This strategy can provide new insights into the design and synthesis of high-performance Li-rich layered oxide cathode materials.

Rational design of practical layered transition metal oxide cathode materials for sodium-ion batteries

Rational design of practical layered transition metal oxide cathode materials for sodium-ion batteries

Cut-off voltage influencing the voltage decay of single crystal lithium-rich manganese-based cathode materials in lithium-ion batteries

The voltage decay of Li-rich layered oxide cathode materials results in the deterioration of cycling performance and continuous energy loss, which seriously hinders their application in the high-energy–density lithium-ion battery (LIB) market. However, the origin of the voltage decay mechanism remains controversial due to the complex influences of transition metal (TM) migration, oxygen release, indistinguishable surface/bulk reactions and the easy intra/inter-crystalline cracking during cycling. We investigated the direct cause of voltage decay in micrometer-scale single-crystal Li1.2Mn0.54Ni0.13Co0.13O2 (SC-LNCM) cathode materials by regulating the cut-off voltage. The redox of TM and O2− ions can be precisely controlled by setting different voltage windows, while the cracking can be restrained, and surface/bulk structural evaluation can be monitored because of the large single crystal size. The results show that the voltage decay of SC-LNCM is related to the combined effect of cation rearrangement and oxygen release. Maintaining the discharge cutoff voltage at 3 V or the charging cutoff voltage at 4.5 V effectively mitigates the voltage decay, which provides a solution for suppressing the voltage decay of Li-rich and Mn-based layered oxide cathode materials. Our work provides significant insights into the origin of the voltage decay mechanism and an easily achievable strategy to restrain the voltage decay for Li-rich and Mn-based cathode materials.

New Insight into Bulk Structural Degradation of High-Voltage LiCoO2 at 4.55 V.

The aggravated mechanical and structural degradation of layered oxide cathode materials upon high-voltage charging invariably causes fast capacity fading, but the underlying degradation mechanisms remain elusive. Here we report a new type of mechanical degradation through the formation of a kink band in a Mg and Ti co-doped LiCoO2 cathode charged to 4.55 V (vs Li/Li+). The local stress accommodated by the kink band can impede crack propagation, improving the structural integrity in a highly delithiated state. Additionally, machine-learning-aided atomic-resolution imaging reveals that the formation of kink bands is often accompanied by the transformation from the O3 to O1 phase, which is energetically favorable as demonstrated by first-principles calculations. Our results provide new insights into the mechanical degradation mechanism of high-voltage LiCoO2 and the coupling between electrochemically triggered mechanical failures and structural transition, which may provide valuable guidance for enhancing the electrochemical performance of high-voltage layered oxide cathode materials for lithium-ion batteries.

Approaching Ultimate Synthesis Reaction Rate of Ni-Rich Layered Cathodes for Lithium-Ion Batteries

HighlightsA series of layered oxide cathode materials were synthesized by high-temperature shock strategy for the first time.The approaching ultimate solid reaction rate of the layered nickel-rich layered oxide LiNixCoyMnzO2 was investigated for the first time. Ultrafast average reaction rate of phase transition from Ni0.6Co0.2Mn0.2(OH)2 to Li-containing oxides is 66.7 (% s-1), that is, taking only 1.5 s.