Synthesis–structure relationships in Li- and Mn-rich layered oxides: phase evolution, superstructure ordering and stacking faults

Menon, Ashok S.; Khalil, Said A.; Ojwang, Dickson O.; Edström, Kristina; Gómez, Cesar Pay; Brant, William R.

doi:10.1039/d2dt00104g

Cited by 10 publications

(8 citation statements)

References 37 publications

(61 reference statements)

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“…[27][28][29][30][31][32][33] To determine the degree of antisite defects, it is possible to make an estimation from the amplitude of the (020) diffraction peak. [34,35] This (020) amplitude value is inversely proportional to the degree of cation mixing, and the trend observed for the values for these materials (0.031, 0.029, and 0.028 for LMRÀ Cu-1, LMRÀ Cu-2, and LMR, respectively) indicates copper doping has decreased the degree of cation mixing (thus improving stability), especially in the case of LMRÀ Cu-1.…”

Section: Chemelectrochemmentioning

confidence: 79%

Effects of Copper Doping in High‐Rate, Lithium Manganese‐Rich Layered Oxide Cathodes for Lithium‐Ion Batteries

Cabello,

Drewett,

Aduviri

et al. 2023

ChemElectroChem

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Lithium manganese‐rich layered oxides are promising cathode materials for lithium‐ion batteries due to their high discharge capacity, but they suffer from capacity fading and poor rate performance. Herein we report on the physicochemical and electrochemical properties of Li1.15Mn0.7Ni0.2Co0.1O2 synthesized via a sol gel method, and study the effect of copper doping on the resulting materials. Electrochemical testing at 1 C revealed 1 % Cu doping enhanced capacity retention (from 58 % to 78 %) but also decreased capacity, while in contrast 10 % Cu doping increased capacity by 21 %. Thorough characterization (including x‐ray diffraction, scanning electron microscopy, inductively coupled plasma‐optical emission spectroscopy, and electrochemical analyses such as voltage vs. capacity and dQ/dV plots) was employed to understand these results, which may be attributed to the competition of two different phenomena depending on the copper content. Consequently, this work highlights the importance of targeting bespoke stoichiometries depending on the desired electrochemical characteristics – an important point for the future design of materials for fast charging and high power applications.

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Section: Chemelectrochemmentioning

confidence: 79%

Effects of Copper Doping in High‐Rate, Lithium Manganese‐Rich Layered Oxide Cathodes for Lithium‐Ion Batteries

Cabello,

Drewett,

Aduviri

et al. 2023

ChemElectroChem

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“…The development of synthesis-defect-structure relationships for oxides using solution-based methods requires careful experimental control and tuning. Well-planned studies can often yield clear results about how subtle changes such as the stirring rate, pH ramp, temperature ramp, or annealing temperature can influence the formation of extended defects [91]. In this context, a rigorous study which utilizes design of experiments [92] together with a quantitative descriptor of stacking faults in the resultant oxide may yield significant advancements.…”

Section: Advances In Science and Technology To Meet Challengesmentioning

confidence: 99%

Roadmap on exsolution for energy applications

et al. 2023

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Over the last decade, exsolution has emerged as a powerful new method for decorating oxide supports with uniformly dispersed nanoparticles for energy and catalytic applications. Due to their exceptional anchorage, resilience to various degradation mechanisms, as well as numerous ways in which they can be produced, transformed and applied, exsolved nanoparticles have set new standards for nanoparticles in terms of activity, durability and functionality. In conjunction with multifunctional supports such as perovskite oxides, exsolution becomes a powerful platform for the design of advanced energy materials. In the following sections, we review the current status of the exsolution approach, seeking to facilitate transfer of ideas between different fields of application. We also explore future directions of research, particularly noting the multi-scale development required to take the concept forward, from fundamentals through operando studies to pilot scale demonstrations.

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“…[16,32,33] Moreover, structural properties vary with the composition and with the synthetic technique used, from precursor mixing and annealing conditions. [34][35][36][37] The structural ambiguity of LRLOs directly reflex on to the sluggish rationalization of the corresponding redox mechanism in batteries and the unsatisfactory comprehension of the structural evolution occurring during repeated cycles of electrochemical lithiumions extraction/insertion. In the figure 2a the typical potential profile of the first cycle obtained is shown for a LRLO with the Li1.2Mn0.54Ni0.13Co0.13O2 stoichiometry.…”

Section: Structure and Reaction Mechanismmentioning

confidence: 99%

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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Synthesis–structure relationships in Li- and Mn-rich layered oxides: phase evolution, superstructure ordering and stacking faults

Abstract: Systematic investigation of synthesis-dependent structural changes in Li- and Mn-rich layered oxides.

Cited by 10 publications

References 37 publications

Effects of Copper Doping in High‐Rate, Lithium Manganese‐Rich Layered Oxide Cathodes for Lithium‐Ion Batteries

Effects of Copper Doping in High‐Rate, Lithium Manganese‐Rich Layered Oxide Cathodes for Lithium‐Ion Batteries

Roadmap on exsolution for energy applications

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

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