Study of the local structure of LiNi0.33+δMn0.33+δCo0.33−2δO2 (0.025≤δ≤0.075) oxides

Ben-Kamel, K.; Amdouni, Noureddine; Mauger, A.; Julien, C.

doi:10.1016/j.jallcom.2012.03.018

Cited by 35 publications

(35 citation statements)

References 36 publications

(30 reference statements)

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“…The fact that for LMR-NMC the "M" in the LiMO 2 is actually a mix of Ni, Mn, and Co would at a minimum cause broadening of the A1g and Eg modes and quite possible split the Eg mode. Ben-Kamel et al 10 accounted for the fact that "M" in LiMO 2 is really three different elements (Ni, Mn, and Co) by assuming that each of the three elements generates a separate A1g and Eg pair and deconvoluted their spectra accordingly. This assumption is most probably an over-simplification of what a thorough lattice dynamics analysis would reveal, hence, as stated above, we have elected to perform our deconvolutions based on convincing visual evidence for the number of bands within the individual band envelopes in Fig.…”

Section: Discussionmentioning

confidence: 99%

“…In a very recent paper Ruther et al 9 conducted Raman examinations of LMR-NMC cells cycled from a discharge voltage of 2.0 V to charging voltages as high as 4.9 V. There results indicated that the structure of the cycled cathode material deviates significantly from the ideal two-component layered phase present in the pristine LMR-NMC cathode. They also highlight the importance of laser power control (to avoid damaging the sample) and sampling over a wide area to assure the gathering of consistent data.In other related studies Ben-Kamel et al 10 employed a combination of XRD and spectroscopic methods (including both Raman and NMR) to investigate the effect of varying Co content on the local structure of as-synthesized LiNi x Co y Mn z O 2 materials with Ni-Mn-Co contents similar to that of HE5050 but without excess lithium. Their results provided evidence of decreasing cation mixing during cycling with increasing Co content.…”

mentioning

confidence: 99%

“…A number of pertinent studies, particularly some of the more recent ones, have employed Raman spectroscopy to elucidate the chemical and structural transformations that the LMR-NMC composition undergoes during electrochemical cycling in cells with lithium-based anodes. [6][7][8][9][10][11][12][13] Amalraj et al 6 used a combination of XRD, TEM, and ex situ Raman spectroscopy to establish that a partial structural transition from a layered-type to a spinel-type of ordering occurred in the initial charge to 4.7 V when their xLi 2 MnO 3 · (1-x)LiMO 2 cathode (M = Ni-Mn-Co) was cycled * Electrochemical Society Active Member.…”

mentioning

confidence: 99%

“…In other related studies Ben-Kamel et al 10 employed a combination of XRD and spectroscopic methods (including both Raman and NMR) to investigate the effect of varying Co content on the local structure of as-synthesized LiNi x Co y Mn z O 2 materials with Ni-Mn-Co contents similar to that of HE5050 but without excess lithium. Their results provided evidence of decreasing cation mixing during cycling with increasing Co content.…”

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A Raman-Based Investigation of the Fate of Li₂MnO₃in Lithium- and Manganese-Rich Cathode Materials for Lithium Ion Batteries

Maroni

Gosztola

et al. 2015

J. Electrochem. Soc.

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The relationship between structure and electrochemical performance of lithium-and manganese-rich cathode materials with the general formula xLi 2 MnO 3 •(1-x)LiMO 2 is under intensive study world-wide in the context of its importance to the development of high energy/high capacity lithium batteries. One of the issues raised in these studies is the fate of the Li 2 MnO 3 component as a function of voltage and repeated cycling. We have performed Raman spectroscopy based measurements that shed light on the transformations of the Li 2 MnO 3 phase as a function of state-of-charge. We find that on charging the Li 2 MnO 3 phase appears to de-lithiate at a rate at least equal to that of the LiMO 2 phase, whereas, on discharge a Li 2 MnO 3 -like component reforms later in the discharge than does the LiMO 2 phase. The absence of X-ray diffraction evidence for the presence of Li 2 MnO 3 after the first charge/discharge cycle can be reconciled by the possibility that the C2/m structured Li 2 MnO 3 exists in domains thick enough to diffract; but during subsequent discharging, a perturbed C2/m phase forms in conjunction with the re-lithiated LiMO 2 phase in thin sheets (electrochemically induced topotaxy) that are not thick enough to diffract but form in sufficient volume to give Raman scattering similar to that of In contrast to conventional layered cathode materials for lithium ion batteries, such as LiNi x Co y Mn z O 2 with x + y + z ∼ = 1.0 leading to an R-3m-like structure, the lithium-and manganese-rich version of this composition (often designated as LMR-NMC) has a layered-layered structure that can be better described as xLi 2 MnO 3 · (1-x)LiMO 2 (M = Ni-Mn-Co).1 It has been clearly demonstrated that this LMR-NMC material consists of not only the R-3m phase but also the Li 2 MnO 3 phase with C2/m structure, with the two structures integrated at the domain level. The two component nature of the pristine material has been investigated by a wide range of techniques, including electrochemistry, X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), transmission electron microscopy (TEM), nuclear magnetic resonance spectroscopy (NMR), and Raman spectroscopy. The high lithium content in the C2/m phase gives LMR-NMC a much higher energy density making it a promising high energy cathode material for lithium ion batteries. Whereas it has been clearly demonstrated that the C2/m phase is no longer detected, e.g., by XRD, after activation at high voltage against lithium (see for example Li et al.2 ), Yu and Yanagida 3 claim evidence for a synergetic relationship between the C2/m component and the R-3m component of LMR-NMC materials wherein the two layered phases stabilize one another during charge and discharge. In prior publications our group showed that the Li 2 MnO 3 component activated in the first charge/discharge cycle is continuously active throughout the whole operating voltage window (2.0 to 4.6 V) during the charge process, but is more active below 3.6 V during the discharge process. [4][5] Ongoing research rela...

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Section: Discussionmentioning

confidence: 99%

mentioning

confidence: 99%

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confidence: 99%

mentioning

confidence: 99%

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A Raman-Based Investigation of the Fate of Li₂MnO₃in Lithium- and Manganese-Rich Cathode Materials for Lithium Ion Batteries

Maroni

Gosztola

et al. 2015

J. Electrochem. Soc.

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“…The lithium-rich Mn-based cathode that contains different transition metals, e.g. Li(Li 0.2 Mn 0.54 Ni 0.13 Co 0.13 ) O 2 offers advantages over compositions containing a single transition metal [11][12][13][14][15][16][17][18]. Both economical and ecological considerations lead to the use of transition metal composites as cathode materials.…”

Section: Introductionmentioning

confidence: 99%

In operando X-ray absorption spectroscopy study of charge rate effects on the atomic environment in graphene-coated Li-rich mixed oxide cathode

et al. 2016

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Li 2 O extraction from the electrode material is known to be a dominant mechanism of irreversible battery capacity loss in the first cycle. The extraction mechanism of the Li + ions shows dependence on the charge rate. Here for the first time we report the difference in the electrochemical behavior at two different charge rates (0.125 C vs 0.5 C) observed using novel design transmission coin cells in the graphene-coated Li(Li 0.2 Mn 0.54 Ni 0.13 Co 0.13 )O 2 cathode by in operando X-ray absorption spectroscopy (XAS). The results obtained from Mn, Co, and Ni atom XANES/EXAFS demonstrate that, whilst during fast charge Li 2 O extraction is localized to the lithium slab in the crystal structure, the delithiation is deeper at the slower charge rate, when Li + ions are removed from both the transition metal and lithium layers. In the slow charge cell, Ni O bond splitting resulting from the Jahn-Teller distortion were clearly identified at approximately 4.224 V when a sudden rise in the bond length was observed in the EXAFS analysis of Mn O and Co O bonds. The results demonstrate the power of using the novel cell design for transmission in operando XAS.

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Regulation of Surface Defect Chemistry toward Stable Ni‐Rich Cathodes

et al. 2022

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Surface reconstruction of Ni‐rich layered oxides (NLO) degrades the cycling stability and safety of high‐energy‐density lithium‐ion batteries (LIBs), which challenges typical surface‐modification approaches to build a robust interface with electrochemical activity. Here, a strategy of leveraging the low‐strain analogues of Li‐ and Mn‐rich layered oxides (LMR) to reconstruct a stable surface on the Ni‐rich layered cathodes is proposed. The new surface structure not only consists of a gradient chemical composition but also contains a defect‐rich structure regarding the formation of oxygen vacancies and cationic ordering, which can simultaneously facilitate lithium diffusion and stabilize the crystal structure during the (de)lithiation. These features in the NLO lead to a dramatic improvement in electrochemical properties, especially the cyclability under high voltage cycling, exhibiting the 30% increase in capacity retention after 200 cycles at the current density of 1 C (3.0–4.6 V). The findings offer a facile and effective way to regulate defect chemistry and surface structure in parallel on Ni‐rich layered structure cathodes to achieve high‐energy density LIBs.

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Study of the local structure of LiNi0.33+δMn0.33+δCo0.33−2δO2 (0.025≤δ≤0.075) oxides

Cited by 35 publications

References 36 publications

A Raman-Based Investigation of the Fate of Li₂MnO₃in Lithium- and Manganese-Rich Cathode Materials for Lithium Ion Batteries

A Raman-Based Investigation of the Fate of Li₂MnO₃in Lithium- and Manganese-Rich Cathode Materials for Lithium Ion Batteries

In operando X-ray absorption spectroscopy study of charge rate effects on the atomic environment in graphene-coated Li-rich mixed oxide cathode

Regulation of Surface Defect Chemistry toward Stable Ni‐Rich Cathodes

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Study of the local structure of LiNi0.33+δMn0.33+δCo0.33−2δO2 (0.025≤δ≤0.075) oxides

Cited by 35 publications

References 36 publications

A Raman-Based Investigation of the Fate of Li2MnO3in Lithium- and Manganese-Rich Cathode Materials for Lithium Ion Batteries

A Raman-Based Investigation of the Fate of Li2MnO3in Lithium- and Manganese-Rich Cathode Materials for Lithium Ion Batteries

In operando X-ray absorption spectroscopy study of charge rate effects on the atomic environment in graphene-coated Li-rich mixed oxide cathode

Regulation of Surface Defect Chemistry toward Stable Ni‐Rich Cathodes

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A Raman-Based Investigation of the Fate of Li₂MnO₃in Lithium- and Manganese-Rich Cathode Materials for Lithium Ion Batteries

A Raman-Based Investigation of the Fate of Li₂MnO₃in Lithium- and Manganese-Rich Cathode Materials for Lithium Ion Batteries