Impact of Overlithiation and Al doping on the battery performance of Li-rich layered oxide materials

Celeste, Arcangelo; Girardi, Fabio; Gigli, Lara; Pellegrini, Vittorio; Silvestri, Laura; Brutti, Sergio

doi:10.1016/j.electacta.2022.140737

Cited by 24 publications

(18 citation statements)

References 51 publications

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“…In LRLO the probability of the occurrence of repeated vicinal LiTM 6 motifs is neither null nor unitary, thus leading to an intermediate lattice where rhombohedral symmetries coexist with limited monoclinic features [23,40] . The achievement of a well‐ordered layered structure is confirmed by the splitting of the (006)/(102) and (108)/(110) pair of peaks, [32,41,42] indexed by the rhombohedral structure. No phase impurity is detected by diffraction in all samples, indicating the high purity of the synthesized materials, either undoped or Fe‐doped.…”

Section: Resultsmentioning

confidence: 99%

“…[27][28][29][30][31] In this context, also our group proved that the over-lithiation combined with Al doping could be a good strategy to mitigate the voltage decay upon cycling in battery and improve the structural stability. [32,33] In this study, we investigate the effect of iron doping on the electrochemical and chemical-physical properties of an overlithiated LRLO. In fact, Fe-doping helps to mitigate the draw-backs of LRLOs due to the stabilization of the structure through a mitigation of electronic disorder.…”

Section: Introductionmentioning

confidence: 99%

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Understanding the Impact of Fe‐Doping on the Structure and Battery Performance of a Co‐Free Li‐Rich Layered Cathodes

et al. 2023

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A series of Co‐free Li‐rich layered oxides, Li1.24Mn0.62‐xNi0.14FexO2 (x=0, 0.01, 0.02 and 0.03) has been synthetized by a self‐combustion reaction. Fe doping affects either lattice structure and bonding as shown by the changes in the size of unit cell calculated from diffraction patterns and in the vibrational frequencies observed in Raman spectra. The electrochemical performance has been evaluated in a lithium cell by galvanostatic cycling: Doped samples show better capacity retention and minor decreases in the specific capacity (i. e., Li1.24Mn0.60Ni0.14Fe0.02O2 can supply a specific capacity of 235 mAhg−1 with 94 % of capacity retention after 150 cycles). These positive effects originated by alterations in the point defectivity (Ni3+ concentration, anionic and cationic vacancies), changes in the transport properties, as showed by Cyclic Voltammetry; as well as an improved structural resilience compared to the un‐doped material in postmortem analyses.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Understanding the Impact of Fe‐Doping on the Structure and Battery Performance of a Co‐Free Li‐Rich Layered Cathodes

et al. 2023

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“…The densified phase grows from the surface while the inner of the particles does not change. Recently, Celeste et al [63,64] extended the analysis beyond the first cycle on Li1.2Mn0.54Ni0.13Co0.13O2 and Li1.28Mn0.54Ni0.13Co0.02Al0.03O2 using XRD and Raman Spectroscopy. From the XRD analysis, the patterns showed the formation of a new phase during the first charge with a very similar structure to the pristine one.…”

Section: Structure and Reaction Mechanismmentioning

confidence: 99%

“…Remarkably Celeste et al proved by Raman spectroscopy the appearance of a peak shoulder possibly attributed to the spinel-distortion, thus suggesting even more complex multiphase mechanisms from the inner core to outer layers of the primary particles of LRLOs. [63,64]…”

Section: Structure and Reaction Mechanismmentioning

confidence: 99%

“…They demonstrated that the presence of Al improves the structural stability while the Zr enhances the specific capacity and the lithium diffusion. Celeste et al [63,97] focused on the substitution of cobalt with lithium (over-lithiation) and aluminium, leading to a family of materials with general formula Li1.2+xMn0.54Ni0.13Co0.13-x-yAlyO2, where 0.03≤x ≤0.08 and 0.03≤y ≤0.05. Apparently, the decrease of the cobalt content leads to an expansion of the unit cell, due to the huge difference in the ionic radius of Co 3+ and Li + .…”

Section: Co-poor Lrlosmentioning

confidence: 99%

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Li-Rich Layered Oxides: Structure and Doping Strategies to Enable Co-poor/Co-free Cathodes for Li-Ion Batteries

Silvestri¹,

Tuccillo²,

Celeste³

et al. 2022

Preprint

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Lithium rich layered oxides (LRLO) are a wide class of innovative active materials for positive electrodes in lithium-ion (LIB) and lithium-metal secondary batteries (LMB). LRLOs are over-stoichiometric layered oxides rich in lithium and manganese, with general formula Li1+xTM1-xO2, where TM is a blend of transition metals comprising Mn (main constituent), Ni, Co, Fe and others. Due to the very variable composition and the extended defectivity their structural identity is still debated among researchers being likely an unresolved hybrid between a monoclinic (mC24) and a hexagonal lattice (hR12). Once casted in composite positive electrode films and assembled in LIBs or LMBs, LRLOs can delivery reversible specific capacities above 220-240 mAhg-1, thus beyond any other available intercalation cathode material for LIBs, with mean working potential above 3.3-3.4 V vs Li for hundreds of cycles in liquid aprotic commercial electrodes. In this review we critically outline the recent advancements in the fundamental understanding of the physico-chemical properties of LRLO as well as the most exciting innovations in their battery performance. We focus in particular on the elusive structural identity of these phases, on the complexity of the reaction mechanism in batteries as well as on practical strategies to minimize or remove cobalt from the lattice while preserving the outstanding performance upon cycling.

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The ENEA′s 2019–2021 Three‐Year Research Project on Electrochemical Energy Storage

et al. 2023

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This work describes the research activities carried out by ENEA in the three-year period 2019-2021 as a part of the Electrochemical Storage project. The project was part of a larger and more integrated project for energy storage, itself contained in the Electric System Research program. Within the project, various research lines were carried out: From the development of materials for electrodes to the testing of electrolytes and separators, both for lithium and sodium-ion batteries, evaluation of the use of lithium metal batteries, and studying how to give a second life to used batteries. Dissemination of the results was an integral part of the program. The reasons that have been adduced to articulate the research plan and the main results obtained are reviewed in this concept.

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Impact of Overlithiation and Al doping on the battery performance of Li-rich layered oxide materials

Cited by 24 publications

References 51 publications

Understanding the Impact of Fe‐Doping on the Structure and Battery Performance of a Co‐Free Li‐Rich Layered Cathodes

Understanding the Impact of Fe‐Doping on the Structure and Battery Performance of a Co‐Free Li‐Rich Layered Cathodes

Li-Rich Layered Oxides: Structure and Doping Strategies to Enable Co-poor/Co-free Cathodes for Li-Ion Batteries

The ENEA′s 2019–2021 Three‐Year Research Project on Electrochemical Energy Storage

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