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At least 307 records · Page 17

In Situ Construction of Uniform and Robust Cathode–Electrolyte Interphase for Li-Rich Layered Oxides

The high-energy-density Li-rich layered oxides (LLOs) as promising cathodes for Li-ion batteries suffer from the dissolution of transition metals (especially manganese) and severe side reactions in conventional electrolytes, which greatly deteriorate their electrochemical performance. Herein, an in situ “anchoring + pouring” synergistic cathode-electrolyte interphase (CEI) construction is realized by using 1,3,6-hexanetricarbonitrile (HTCN) and tris(trimethylsilyl) phosphate (TMSP) electrolyte additives to alleviate the challenges of an LLO (Li 1.13 Mn 0.517 Ni 0.256 Co 0.097 O 2 ). HTCN with three nitrile groups can tightly anchor transition metals by coordinative interaction to form the CEI framework, and TMSP will electrochemically decompose to reshape the CEI layer. The uniform and robust in situ constructed CEI layer can suppress the transition metal dissolution, shield the cathode against diverse side reactions, and significantly improve the overall electrochemical performance of the cathode with a discharge voltage decay of only 0.5 mV/cycle -1 . Further investigations based on a series of experimental techniques and theoretical calculations have revealed the composition of in situ constructed CEI layers and their distribution, including the enhanced HTCN anchoring effect after lattice densification of LLOs. Finally, this study provides insights into the in situ CEI construction for enhancing the performance of high-energy and high-voltage cathode materials through effective, convenient and economical electrolyte approaches.

25 ENERGY STORAGE↗

Lattice Oxygen Redox Reversibility Modulation in Enhancing the Cycling Stability of Li-Rich Cathode Materials

The practical application of lithium-rich layered oxides is prohibited by the drawbacks such as severe capacity and voltage degradation resulting from unstable oxygen redox environment and the accompanied irreversible oxygen release. In this report a facile and effective strategy is proposed to regulate the oxygen redox chemistry via foreign Fe doping and its induced intrinsic transition metal (TM) doping as well as the in situ constructed spinel surface layer. The Fe doping, together with the induced intrinsic TM dual doping, can stabilize the lattice oxygen in the bulk due to the formed stronger Fe—O bond, and restrain the irreversible TM migration and then the undesirable phase transformation. More importantly, thermodynamical energy barrier of oxygen activation is dramatically decreased by the O 2p–Fe 3d charge-transfer, allowing stable oxygen redox activity. And the pre-constructed spinel layer can effectively stabilize the surface lattice oxygen and suppress harmful interfacial side-reactions. Such a simple optimizing method make the modified cathode exhibit a high specific capacity of 298 mAh g -1 at 0.2 C, outstanding cycling stability with a superior capacity and voltage retentions of 92.5% and 90.8%, respectively, after 400 cycles at 1 C. This study provides a new direction for developing advanced Li-ion batteries.

25 ENERGY STORAGE↗

Enabling Structure/Interface Regulation for High Performance Ni-Rich Cathodes

Here, further commercialization of Ni-rich layered cathodes is hindered by severe structure/interface degradation and kinetic hindrance that occur during electrochemical operation, which leads to safety risks and reduced range in electric vehicles (EVs). Herein, by selecting elements with different solubility properties, a multifunctional strategy that synchronously fabricates perovskite-type SrZrO 3 coating and Sr/Zr co-doping is employed to strengthen the structure/interface stability and the Li + transport mobility of LiNi 0.85 Co 0.10 Mn 0.05 O 2 (NCM). Perovskite-type SrZrO 3 protective layers formed on the particle surface can substantially mitigate the unexpected interfacial side reactions and surface phase transitions. In addition, a robust crystal framework is constructed by optimizing local O coordination through the introduction of strong Zr-O bonds. Notably, Li + diffusion kinetics is effectively improved due to expanded cell parameters and O-Li-O slab spacing with the incorporation of large-diameter Sr pillar ions, as revealed by X-ray diffraction. As a result, the Sr/Zr-modified NCM achieves a remarkable capacity retention of 99.4% after 200 cycles at 1 C, and a high rate capacity of 168.9 mAh g -1 at 10 C. This work opens new avenues to develop high-performance NCM cathodes with high energy and high power for EVs with long calendar life.

25 ENERGY STORAGE↗

Structural and Chemical Evolution of Highly Fluorinated Li‐Rich Disordered Rocksalt Oxyfluorides as a Function of Temperature

Abstract Li‐rich disordered rocksalt (DRS) oxyfluorides have emerged as promising high‐energy cathode materials for lithium‐ion batteries. While a high level of fluorination in DRS materials offers performance advantages, it can only be achieved via mechanochemical synthesis, which poses challenges of reproducibility and scalability. The definition of relationships between fluorination and structural stability is required to devise alternative methods that overcome these challenges. In this study, the thermal evolution of three highly fluorinated phases, Li 2 TMO 2 F (TM = Mn, Co, and Ni), is investigated in an inert atmosphere. Diffraction and spectroscopic techniques are utilized to examine their electronic and chemical states up until conditions of decomposition. The analysis reveals that the materials phase‐separate above 400 °C, at most. It is also observed that heat‐treated DRS materials exhibit intricate changes in the local coordination of the metals, including their spin, and ordering compared to the pristine states. The changes upon annealing are accompanied by a modulation of the voltage profile, including reduced hysteresis, when used as electrodes. These results provide an in‐depth understanding of the fundamental crystal chemistry of DRS oxyfluorides in view of their promising role as the next generation of Li‐ion cathodes.

25 ENERGY STORAGE↗

Full Concentration Gradient-Tailored Li-Rich Layered Oxides for High-Energy Lithium-Ion Batteries

Lithium-rich layered oxides (LLOs) are prospective cathode materials for next-generation lithium-ion batteries (LIBs), but severe voltage decay and energy attenuation with cycling still hinder their practical applications. In this study, a series of full concentration gradient-tailored agglomerated-sphere LLOs are designed with linearly decreasing Mn and linearly increasing Ni and Co from the particle center to the surface. The gradient-tailored LLOs exhibit noticeably reduced voltage decay, enhanced rate performance, improved cycle stability, and thermal stability. Without any material modifications or electrolyte optimizations, the gradient-tailored LLO with medium-slope shows the best electrochemical performance, with a very low average voltage decay of 0.8 mV per cycle as well as a capacity retention of 88.4% within 200 cycles at 200 mA g –1 . These excellent findings are due to spinel structure suppression, electrochemical stress optimization, and Jahn-Teller effect inhibition. Further investigation shows that the gradient-tailored LLO reduces the thermal release percentage by as much as about 41% when the battery is charged to 4.4 V. This study provides an effective method to suppress the voltage decay of LLOs for further practical utilization in LIBs and also puts forward a bulk-structure design strategy to prepare better electrode materials for different rechargeable batteries.

36 MATERIALS SCIENCE↗

Quantitative Identification of Dopant Occupation in Li‐Rich Cathodes

Elemental doping is widely used to improve the performance of cathode materials in lithium‐ion batteries. However, macroscopic/statistical investigation on how doping sites are distributed in the material lattice, despite being a key prerequisite for understanding and manipulating the doping effect, has not been effectively established. Herein, to solve this predicament, a universal strategy is proposed to quantitatively identify the locations of Al and Mg dopants in lithium‐rich layered oxides (LLOs). Solid evidence confirms that Al prefers to occupy the transition metal (TM) layer, while Mg evenly occupies both TM and Li layers. As a result, Mg significantly reduces the thickness of LiO 2 slabs at room temperature, which will increase the energy barrier of oxygen activation and enhance the structure stability of LLOs. The suppressed oxygen activity in Mg‐doped LLO can be kinetically unlocked at 55 °C. The different characteristics of Al and Mg enlighten an Al/Mg co‐doping strategy to optimize LLOs, which significantly improves the cycle performance while lifting the capacity. In conclusion, these insights from the quantitative identification of doping sites shed light on the manipulation of doping effects toward better cathodes.

25 ENERGY STORAGE↗

Kinetically Dormant Ni‐Rich Layered Cathode During High‐Voltage Operation

Abstract The degradation of Ni‐rich cathodes during long‐term operation at high voltage has garnered significant attention from both academia and industry. Despite many post‐mortem qualitative structural analyses, precise quantification of their individual and coupling contributions to the overall capacity degradation remains challenging. Here, by leveraging multiscale synchrotron X‐ray probes, electron microscopy, and post‐galvanostatic intermittent titration technique, the thermodynamically irreversible and kinetically reversible capacity loss is successfully deconvoluted in a polycrystalline LiNi 0.83 Mn 0.1 Co 0.07 O 2 cathode during long‐term charge/discharge cycling in full cell configuration. Contradicting the dramatic capacity loss, the layered structure remains highly alive even after 1000 cycles at 4.6 V while undergoing a three‐order of magnitude reduction in the mass transfer kinetics, leading to almost fully recoverable capacity under kinetic‐free conditions. Such kinetic dormant behavior after cycling is not simply ascribed to poor chemical diffusion by reconstructed cathode surface but highly synchronizes with the lattice strain evolution stemming from the structural heterogeneity between deeply delithiated layered and degraded rock‐salt phases at high voltage. These findings deepen the degradation mechanism of high‐voltage cathodes to achieve long‐cycling and fast‐charging performance.

36 MATERIALS SCIENCE↗

Tailoring the Reaction Heterogeneity for Robust Li‐Rich Cathodes

The practical application of Li-rich Mn-based layered oxides (LLO) cathode is hindered by severe capacity and voltage degradation resulting from severe oxygen release and irreversible phase transition. In this work, the reaction heterogeneity, which describes the spatially resolved electrochemical divergence within individual cathode particles, is engineered through compositional gradient design to couple Li + transport kinetics and the anion redox activity between particle interiors and surfaces. It is revealed that Co/Mn concentration gradient within particles creates heterogeneous phase content distribution and structural ordering, inducing surface-bulk reaction heterogeneity that significantly impacts the overall electrochemical performance. Specifically, Li 2 MnO 3 -poor and Co-enriched surface effectively mitigates the oxygen loss and enhances electrochemical reaction kinetics, benefited from the reduced surface redox reactivity and induced highly ordered intra-layered cationic arrangement. Meanwhile, the Li 2 MnO 3 -enriched core with slight Li/Ni intermixing provides high reversible capacity and strong mechanical stability. Consequently, the greatly enhanced anion redox reversibility, Li + diffusion dynamics, and structure stability endow LLO with exceptional electrochemical properties, showing a capacity retention of 86.0% and a reduced voltage decay of 0.518 mV per cycle after 500 cycles at 1 C. This work provides a valuable strategy to tailor the redox chemistry and achieve robust LLO.

25 ENERGY STORAGE↗

Complex-Concentrated Anion Doping Enables Ultra-Stable Lattice Oxygen and Structural Integrity in Lithium-Rich Layered Oxide Cathodes

Lithium- and manganese-rich layered oxides (LMR) stand out as next-generation lithium-ion cathode chemistries, which harness both transition-metal and lattice-oxygen redox processes to deliver exceptional capacity and energy density. However, their full potential is hindered by intrinsic oxygen instability and structural degradation, resulting in pronounced voltage fade and capacity decay. Here, we present a complex-concentrated anion-doping paradigm in which multiple anions, F, Br, and S, are incorporated into the oxygen sublattice to enhance oxygen-redox and structural stability. X-ray absorption spectroscopy and aberration-corrected scanning transmission electron microscopy confirm ultra-stable local oxygen coordination environments during long-term cycling, with detrimental phase transformations and oxygen-loss-induced cavitation dramatically inhibited. Notably, we show that the characteristic LiTM6 transition metal (TM) honeycomb ordering is preserved even after electrochemical cycling. Concurrently, this strategy yields an unprecedented volume change of only 0.63% upon charging to 4.8 V vs. Li+/Li, achieving the first zero-strain LMR cathode. The resulting LMR cathode delivers ultralow voltage fade (1 mV per cycle during the first 100 cycles and becomes negligible in subsequent cycles) and outstanding energy retention (93% after 200 cycles) in a pouch cell configuration. Our complex-concentrated anion-doping concept establishes a broadly applicable strategy for resolving chemo-mechanical failure mechanisms in ceramic intercalation electrodes for next-generation energy storage.

Li-ion batteries↗

Tracking the Influence of Thermal Expansion and Oxygen Vacancies on the Thermal Stability of Ni-Rich Layered Cathode Materials

The ever-growing demand for high-energy lithium-ion batteries in portable electronics and electric vehicles has triggered intensive research efforts over the past decade. An efficient strategy to boost the energy and power density of lithium-ion batteries is to increase the Ni content in the cathode materials. However, a higher Ni content in the cathode materials gives rise to safety issues. Herein, thermal expansion and oxygen vacancies are proposed as new critical factors that affect the thermal stability of charged Ni-rich cathode materials based on a systematic synchrotron-based X-ray study of Li 0.33 Ni 0.5+x Co 0.2 Mn 0.3-x O 2 (x = 0, 0.1, 0.2) cathode materials during a heating process. Charged cathode materials with higher Ni contents show larger thermal expansion, which accelerates transition metal migration to the Li layers. Oxygen vacancies are formed and accumulate mainly around Ni ions until the layered-to-spinel phase transition begins. The oxygen vacancies also facilitate transition metal migration to the Li layers. Thermal expansion and the presence of oxygen vacancies decrease the energy barrier for cation migration and facilitate the phase transitions in charged cathode materials during the heating process. These results provide valuable guidance for developing new cathode materials with improved safety characteristics.

25 ENERGY STORAGE↗

Regulating the Electron Distribution of Metal-Oxygen for Enhanced Oxygen Stability in Li-rich Layered Cathodes

Li-rich Mn-based layered oxides (LLO) hold great promise as cathode materials for lithium-ion batteries (LIBs) due to their unique oxygen redox (OR) chemistry, which enables additional capacity. However, the LLOs face challenges related to the instability of their OR process due to the weak transition metal (TM)-oxygen bond, leading to oxygen loss and irreversible phase transition that results in severe capacity and voltage decay. Herein, a synergistic electronic regulation strategy of surface and interior structures to enhance oxygen stability is proposed. In the interior of the materials, the local electrons around TM and O atoms may be delocalized by surrounding Mo atoms, facilitating the formation of stronger TM—O bonds at high voltages. Besides, on the surface, the highly reactive O atoms with lone pairs of electrons are passivated by additional TM atoms, which provides a more stable TM—O framework. Hence, this strategy stabilizes the oxygen and hinders TM migration, which enhances the reversibility in structural evolution, leading to increased capacity and voltage retention. This work presents an efficient approach to enhance the performance of LLOs through surface-to-interior electronic structure modulation, while also contributing to a deeper understanding of their redox reaction.

25 ENERGY STORAGE↗

Single-Crystalline Ni-Rich LiNi x Mn y Co 1– x – y O 2 Cathode Materials: A Perspective

To drive electrical vehicles for long-range, the energy density of Li-ion batteries must be further enhanced, which requires high-energy cathode materials. Among them, Ni-rich LiNi x Mn y Co 1–x–y O 2 (x > 0.5, NMC) is one of the most promising candidates. However, traditional poly-crystal (PC) NMC materials, whose particles are secondary clusters consisting of many primary crystalline particles, are susceptible to pulverization along the inter grain/particle boundaries, resulting in poor cycle stability. Recently, single crystal (SC)-NMC cathodes are proposed as they are believed to have several merits such as high structural integrity, lower interface with electrolyte, and potentially better energy storage performance. Nevertheless, several queries, such as the merits of SC structure and the mechanism for their structure degradation, are still controversial and required to be addressed. Here, in this study, the synthesis parameters, properties, energy storage as well as safety of SC- and PC-NMC cathodes with various Ni contents are critically reviewed, for clarifying the merits and drawbacks of SC. Furthermore, the study focuses on the recent advances of insight mechanisms and strategies for stabilizing the structure/interface by doping, morphology engineering, surface coating, and composition tailoring. The remaining challenges, safety concerns, and perspectives to enhance the electrochemical performance of SC-NMC cathodes for electric vehicle application are followed.

25 ENERGY STORAGE↗

Upgrading the Performance and Stability of Lithium, Manganese-Rich Layered Oxide Cathodes with Combined-Formic Acid and Spinel Coating Treatment

We report improving sluggish rate performance and cycling stability of Li, Mn-rich cathode materials (LMR) is of great importance for practical implementation. Here, dual surface modification on LMR particles with formic acid washing and spinel coating improves the electrochemical performance. Dilute formic acid can remove the Li2CO3 surface impurities and selectively reduce Ni while significantly increasing specific surface area by ~32 %, unlocking more electrochemically active surfaces. Spinel coating enhances cycle stability by suppressing detrimental side reactions at electrode-electrolyte interfaces at high voltage. Post-annealing temperature was found to significantly affect the cathode performance. Higher temperature favors diffusion of transition metal (TM)/Li ions of the spinel coating from surface to the bulk, removing the coating by possible reconstruction into the layered structure and thus degrading the performance. The spinel coating also appears to increase Co 3+ segregation on the particle surface. Compared to the original material, the optimized sample demonstrates 47 % higher capacity retention at 3C and retains 89 % of initial capacity after 150 cycles at 0.5C. Besides, the specific energy density of 523 Wh kg -1 can be attained after 150 cycles at 0.5C. Moreover, the post-cycling analysis of modified sample verifies a better structural integrity with less particle cracking. Altogether, this study portrays an alternative strategy to overcome the shortcomings of LMR cathode materials.

25 ENERGY STORAGE↗

Surface Modification of Nickel-Rich Cathode Materials by Ionically Conductive Materials at Room Temperature

Nickel-rich cathode materials (LiNi x Mn y Co 1-x-y O 2 , NMC) are promising to push the limits of lithium-ion batteries to higher energy density. This approach is favored in practical applications including electric vehicles and aviation transportation. However, the instability of the NMC at charged state results in safety concerns and poor cycling stability. Surface coating is a practical and effective strategy to address this. Cubic Li7La3Zr2O12 (LLZO) is an ideal coating material regarding the low electron transfer rate and high Li+ conductivity. Thus, a LLZO coating layer can suppress the parasitic reactions in the electrode/electrolyte interface without deteriorating the lithium migration. However, high-temperature calcination seems to inevitably create the chemical couplings between NMC and LLZO, leading to the interdiffusion and degradation of NMC and LLZO crystal structures. This work presents a simple mechanochemical method to effectively coat LLZO on the NMC particle surface. Furthermore, the coated cathode demonstrates superior electrochemical performance compared with the pristine NMC cathode.

25 ENERGY STORAGE↗

Correlating Rate-Dependent Transition Metal Dissolution between Structure Degradation in Li-Rich Layered Oxides

Understanding the mechanism of the rate-dependent electrochemical performance degradation in cathodes is crucial to developing fast charging/discharging cathodes for Li-ion batteries. Here, in this work, taking Li-rich layered oxide Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 as the model cathode, the mechanisms of performance degradation at low and high rates are comparatively investigated from two aspects, the transition metal (TM) dissolution and the structure change. Quantitative analyses combining spatial-resolved synchrotron X-ray fluorescence (XRF) imaging, synchrotron X–ray diffraction (XRD) and transmission electron microscopy (TEM) techniques reveal that low-rate cycling leads to gradient TM dissolution and severe bulk structure degradation within the individual secondary particles, and especially the latter causes lots of microcracks within secondary particles, and becomes the main reason for the fast capacity and voltage decay. In contrast, high-rate cycling leads to more TM dissolution than low-rate cycling, which concentrates at the particle surface and directly induces the more severe surface structure degradation to the electrochemically inactive rock-salt phase, eventually causing a faster capacity and voltage decay than low-rate cycling. These findings highlight the protection of the surface structure for developing fast charging/discharging cathodes for Li-ion batteries.

25 ENERGY STORAGE↗

Enhancing the Reaction Kinetics and Stability of Co‐Free Li‐Rich Cathode Materials via a Multifunctional Strategy

Co-free Li-rich layered oxides (CFLLOs) with anionic redox activity are among the most promising cathode materials for high-energy-density and low-cost lithium-ion batteries (LIBs). However, irreversible oxygen release often causes severe structural deterioration, electrolyte decomposition, and the formation of unstable cathode-electrolyte interface (CEI) film with high impedance. Additionally, the elimination of cobalt elements further deteriorates the reaction kinetics, leading to reduced capacity and poor rate performance. Here, in this study, a multifunctional strategy is proposed, incorporating Li 2 MnO 3 phase content regulation, micro-nano structure design, and heteroatom substitution. The increased content of Li 2 MnO 3 phase enhances the capacity through oxygen redox. The smaller nanoscale primary particles induce greater tensile strain and introduce more grain boundaries, thereby improving the reaction kinetics and reactivity, while the larger micron-sized secondary particles help to reduce interfacial side reactions. Furthermore, Na⁺ doping modulates the local coordination environment of oxygen, stabilizing both the anion framework and the crystal structure. As a result, the designed cathode exhibits enhanced rate performance, delivering a capacity of 158 mAh g⁻¹ at 5.0 C and improved cyclic stability, with a high capacity retention of 99% after 400 cycles at 1.0 C. This multifunctional strategy holds great promise for advancing the practical application of CFLLOs in next-generation LIBs.

Co-free Li-rich layered oxide↗

Impacts of Lanthanum Impurities on Nickel-Rich Cathode Materials

The widespread use of lithium-ion batteries (LIBs) has led to environmental concerns and exacerbated the scarcity of essential minerals, underscoring the urgent need for effective recycling strategies. Among various recycling methods, the hydrometallurgical process is distinguished by its energy efficiency and minimal environmental impact. Nickel-metal hydride (Ni-MH) batteries are a significant source of nickel sulfate (NiSO 4 ) for hydrometallurgical recycling due to their substantial nickel content. A significant challenge arises from the effective separation of lanthanum (La), which results in at least 20 ppm of La being present in the recycled NiSO 4 . This study explores a critical aspect of the recycling process: the impact of La 3+ impurities, introduced through recycled NiSO 4 , on the performance of the synthesized nickel-rich cathode materials. We conducted a thorough investigation into how La 3+ influences morphology and structural integrity during both the synthesis of precursors and the production of cathode materials. Our findings indicate that La 3+ impurities do not adversely affect the morphology or structural integrity of the cathode precursors relative to virgin materials. However, higher concentrations of La 3+ reduce the discharge capacity with enhanced cycle stability by minimizing cation mixing between lithium (Li + ) and nickel (Ni 2+ ) ions within the cathode. Furthermore, this stability is crucial for extending battery life. Therefore, controlling the concentration of La 3+ impurities is essential for optimizing the electrochemical performance of recycled cathode materials.

Corrosion↗

Fuel-rich oxidation of gasoline surrogate components in an atmospheric flow reactor

Fuel-rich oxidation of three typical gasoline surrogate components, toluene, isooctane, and n-heptane, was investigated in an atmospheric-pressure flow reactor at mean gas temperatures from 1050 to 1350 K, equivalence ratio of 9.0, and residence times of 0.45 and 1.2 s. Not only polycyclic aromatic hydrocarbons (PAHs) up to 3 ring structure but also small intermediate products from C 1 to C 5 were quantified by a gas chromatograph mass spectrometry coupled with photon ionization and gas chromatograph with flame ionization detector, respectively. The kinetic model recently developed by Lawrence Livermore National Laboratory was revised to reflect the results of many recent investigations. Basically, the updated model could satisfactorily reproduce the experimental mole fractions of many species. The experimental and simulated results showed that PAH mole fractions produced were in the order of toluene, isooctane, and n-heptane. The kinetic analysis using the model was carried out to explore PAH formation pathways, especially focusing on naphthalene, acenaphthylene, and phenanthrene. Through rate of production analysis, it was found that the main formation pathways of many PAHs were affected by the fuels. Although resonantly stabilized radicals, such as benzyl and fulvenallenyl radicals, played a crucial role in the formation pathways of many PAHs in every fuel, they were produced through hydrogen elimination of toluene in toluene fuel, while they were formed from small intermediate products in isooctane and n-heptane fuels. Sensitivity analysis revealed the difference and similarity of the reactions with large positive coefficients according to the fuels studied here. In conclusion, the molecular growth reactions of aromatic species were influential in PAH production in every fuel, whereas the ring formation reactions from small species and the reactions involving toluene had large positive sensitivity coefficients in isooctane/n-heptane and toluene fuels, respectively.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗