Long‐Range Cationic Disordering Induces two Distinct Degradation Pathways in Co‐Free Ni‐Rich Layered Cathodes

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(12)

Published: Dec. 22, 2022

Ni-rich layered oxides are one of the most attractive cathode materials in high-energy-density lithium-ion batteries, their degradation mechanisms still not completely elucidated. Herein, we report a strong dependence pathways on long-range cationic disordering Co-free Li1-m (Ni0.94 Al0.06 )1+m O2 (NA). Interestingly, disordered phase with lattice mismatch can be easily formed near-surface region NA particles very low cation disorder (NA-LCD, m≤0.06) over electrochemical cycling, while structure is basically maintained core forming "core-shell" structure. Such surface reconstruction triggers rapid capacity decay during first 100 cycles between 2.7 and 4.3 V at 1 C or 3 C. On contrary, local distortions gradually accumulated throughout whole higher degrees (NA-HCD, 0.06≤m≤0.15) that lead to slow upon cycling.

Language: Английский

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Enabling Superior Cycling Stability of LiNi_0.9Co_0.05Mn_0.05O₂ with Controllable Internal Strain

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(26)

Published: March 16, 2023

Abstract Intergranular cracking of Ni‐rich layered LiNi 1‐x‐y Co x Mn y O 2 (1‐x‐y ≥ 0.8) cathode particles deteriorate the chemo–electro–mechanical stability high‐energy lithium‐ion batteries (LIBs), thus presenting a challenge to typical modification methods establish robust structures with highly efficient storage. Herein, ZrTiO 4 (ZTO) as an epitaxial layer enhance mechanical ultrahigh‐Ni 0.9 0.05 (NCM90) is reported for first time. Intensive exploration from structure characterizations (X‐ray absorption spectroscopy and in situ X‐ray diffraction techniques), multi‐physics field analysis, first‐principles calculations disclose that conformal ZTO layers Zr doping effectively suppresses internal strain release lattice oxygen, which prodigiously restrains local stress accumulation during whole (de)lithiation processes, thereby maintaining good materials. Meanwhile, protective also prevents electrolyte erosion, keeping intact surface NCM90. Notably, ZTO‐modified NCM90 achieves significantly improved cyclability under high‐voltage (4.5 V) operation, expressing 17% increase capacity retention (71% vs 88%) after 100 cycles. Overall, this work reveals role original degradation behavior effectiveness engineering strategy solve challenge, emphasizing protection mitigates NCM by anchoring oxygen.

Language: Английский

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Sulfide-Based All-Solid-State Lithium–Sulfur Batteries: Challenges and Perspectives

Nano-Micro Letters, Journal Year: 2023, Volume and Issue: 15(1)

Published: March 28, 2023

Lithium-sulfur batteries with liquid electrolytes have been obstructed by severe shuttle effects and intrinsic safety concerns. Introducing inorganic solid-state into lithium-sulfur systems is believed as an effective approach to eliminate these issues without sacrificing the high-energy density, which determines sulfide-based all-solid-state batteries. However, lack of design principles for high-performance composite sulfur cathodes limits their further application. The cathode regulation should take several factors including insulation sulfur, well-designed conductive networks, integrated sulfur-electrolyte interfaces, porous structure volume expansion, correlation between account. Here, we summarize challenges regulating respect ionic/electronic diffusions put forward corresponding solutions obtaining stable positive electrodes. In last section, also outlook future research pathways architecture guide develop

Language: Английский

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Microstructures of layered Ni-rich cathodes for lithium-ion batteries

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4707 - 4740

Published: Jan. 1, 2024

The microstructural degradation, stabilization, and characterization of layered Ni-rich cathodes for Li-ion batteries are comprehensively reviewed in this paper.

Language: Английский

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Enabling an Intrinsically Safe and High‐Energy‐Density 4.5 V‐Class Lithium‐Ion Battery with Synergistically Incorporated Fast Ion Conductors

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(18)

Published: March 3, 2023

Abstract The Ni‐rich layered oxide cathode is pushing the frontier of battery powered electric vehicles toward longer driving range and lower cost, whilst facing a major challenge with compromised cycle life thermal robustness. It well recognized that irreversible oxygen evolution at cathode‐electrolyte interphase critical to electrochemical stability cathode. Herein, combining experiments density functional theory (DFT) calculations, authors focus on manipulating solve performance degradation safety hazard. An ion conductor introduced surface restrains activated surficial lattice ions by its stable vacancies. Meanwhile, Li‐rich fast incorporated in coating layer synergistically reinforces Li diffusion path through interphase. This sophisticated multifunctional modification implemented neat one‐step treatment represents successful design development thermally approximately 400‐cycle state‐of‐health up 80% operating voltage extended 4.5 V. Therefore, this study provides an encouraging strategy overcome capacity versus robustness dilemma high‐energy cathodes.

Language: Английский

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Accessing the O Vacancy with Anionic Redox Chemistry Toward Superior Electrochemical Performance in O3 type Na‐Ion Oxide Cathode

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(32)

Published: April 13, 2024

Abstract Anionic redox chemistry is now viewed as the effective paradigm of improving capacity layered oxide materials in Sodium‐ion battery. In this study, O3‐type NaLi 0.18 Co 0.23 Ru 0.59 O 2 (NLCR) with ability successfully synthesized via a facile solid‐state synthesis method. By manipulating calcinate atmosphere air and argon (sort by NLCR‐Air NLCR‐Ar respectively), large amount vacancy introduced cathode. sufficient exhibited superior rate performance which showed 87.7% retention after 1000 cycles at 20 C. Both activation properties supported soft X‐ray absorption spectroscopy (sXAS). Nevertheless, in‐situ diffraction sXAS studies disclosed can promote reversible phase transition effectively suppress irreversible upon cycling. These are further theoretical study suggested fast kinetic Na diffusion less electron agglomeration around atom for vacancy.The research proposed modification strategy extraordinary property within cathode offered novel insight into understanding anionic mechanism thus provide guidance material design advanced energy storage systems.

Language: Английский

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Insights into the precursor specific surface area for engineering Co-free Ni-rich cathodes with tailorable properties

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 483, P. 149189 - 149189

Published: Feb. 2, 2024

Language: Английский

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Insights into Cation Migration and Intermixing in Advanced Cathode Materials for Lithium‐Ion Batteries

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: unknown

Published: June 29, 2024

Abstract Cathode materials are the core components of lithium‐ion batteries owing to determination practical voltage and effective energy battery system. However, advanced cathodes have faced challenges related cation migration intermixing. In this review, study summarizes structural failure mechanisms due mixing cathodes, including Ni‐rich Li‐rich layered spinel, olivine, disordered rock‐salt materials. This review starts by discussing degradation caused intermixing in different focusing on electronic structure, crystal electrode structure. Furthermore, optimization strategies for inhibition rational utilization systematically encapsulated. Last but not least, remaining proposed perspectives highlighted future development cathodes. The accurate analysis using characterization, precise control material synthesis, multi‐dimensional synergistic modification will be key research areas provides a comprehensive understanding emerge as pivotal controllable factors further

Language: Английский

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Ultrastable cathodes enabled by compositional and structural dual-gradient design

Nature Energy, Journal Year: 2024, Volume and Issue: 9(10), P. 1252 - 1263

Published: Aug. 2, 2024

Language: Английский

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Diffusion-induced stress optimization by boosted surface Li-concentration for single-crystal Ni-rich layered cathodes

Materials Today, Journal Year: 2022, Volume and Issue: 61, P. 40 - 53

Published: Nov. 7, 2022

Language: Английский

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