Different oxygen redox participation for bulk and surface: A possible global explanation for the cycling mechanism of Li1.20Mn0.54Co0.13Ni0.13O2

Koga, Hideyuki; Croguennec, Laurence; Ménétrier, Michel; Mannessiez, Philippe; Weill, François; Delmas, Claude

doi:10.1016/j.jpowsour.2013.02.075

Cited by 299 publications

(395 citation statements)

References 31 publications

Supporting

Mentioning

362

Contrasting

Order By: Relevance

“…25,[27][28][29] However, using a material with a very high lithium content, like the 0.50 Li 2 MnO 3 material in this study, a partial bulk transformation can be observed, amounting to ≈20 mol% of the material being converted into a spinel-like phase (calculated from the oxygen evolution, shown in Model II from Table IV). While the TEM data are statistically not sufficient to provide exact quantitative surface layer thickness values for averaged over the entire material, they fit well to the quantification from the OEMS results.…”

Section: Discussionmentioning

confidence: 73%

“…25 Both observations suggested that the observed oxygen release cannot be ascribed to a loss of oxygen from the bulk of the material, but that the oxygen is only being released from the near-surface Thus, more recent studies propose that bulk and surface of these overlithiated materials show distinctly different properties, rationalized by a bulk-shell model. 25,[27][28][29] It has been suggested that oxygen release takes places in near-surface region, leading to a chemical layered-to-spinel transformation and a concomitant impedance buildup by the formed resistive surface layer. This phenomenon has also been shown to be one of the main fading mechanisms for traditional NCM materials.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Oxygen Release and Surface Degradation of Li- and Mn-Rich Layered Oxides in Variation of the Li₂MnO₃Content

Teufl

Strehle

Müller³

et al. 2018

J. Electrochem. Soc.

157

View full text Add to dashboard Cite

In this study, we will show how the oxygen release depends on the Li 2 MnO 3 content of the material and how it affects the actual voltage fading of the material. Thus, we compared overlithiated NCMs (x Li 2 MnO 3 • (1-x) LiMeO 2 ; Me = Ni, Co, Mn) with x = 0.33, 0.42 and 0.50, focusing on oxygen release and electrochemical performance. We could show that the oxygen release differs vastly for the materials, while voltage fading is similar, which leads to the conclusion that the oxygen release is a chemical material degradation, occurring at the surface, while voltage fading is a bulk issue of these materials. We could prove this hypothesis by HRTEM, showing a surface layer, which is dependent on the amount of oxygen released in the first cycles and leads to an increase of the charge-transfer resistance of these materials. Furthermore, we could quantitatively deconvolute capacity contributions from bulk and surface regions by dQ/dV analysis and correlate them to the oxygen loss. As a last step, we compared the gassing to the base NCM (LiMeO 2 , Me = Ni, Co, Mn), showing that surface degradation follows a similar reaction pathway and can be easily To face future issues, as global warming, air pollution, as well as the consumption of fossil fuels, an alternative is required to cover the future demand of energy and mobility in an environmentally friendly and sustainable way. In this context, lithium-ion batteries are viable options for large scale energy storage and for electric vehicles, as they have been used to power consumer electronics for many years. 1,2Since graphite is an excellent anode material at potentials of ≈0.1 V vs. Li + /Li with a roughly 2-fold higher specific capacity of about 360 mAh/g compared to currently used cathode active materials (CAMs), many efforts have been undertaken to increase the specific capacity and energy density of CAMs. As first practical cathode active material Lithium-Cobalt-Oxide (LCO) was investigated by Goodenough et al. in the 1980s, exhibiting a specific capacity of about 140 mAh/g and having a layered structure composed of lithium and transition metal layers.3 As these layered structures showed good structural stability during lithium extraction and insertion, and therefore good capacity retention, many attempts have been undertaken to further develop alternative layered structures which would offer higher capacity. One promising attempt that led to the currently used Lithium-NickelCobalt-Manganese-Oxides (NCMs) is to change the occupancy of the transition metal layer by not using exclusively cobalt, but also introducing nickel and manganese into the transition metal layer; hereby it was found that nickel shows a high redox activity, while manganese helps to stabilize the structure during lithium extraction.4-6 By using different transition metals and metal compositions, a playground has been created that allows to tune the properties of the material: while initially a Ni:Co:Mn ratio of 1:1:1 was used (also referred to as NCM-111), trends nowadays favor the so-called Ni...

show abstract

Section: Discussionmentioning

confidence: 73%

mentioning

confidence: 99%

Oxygen Release and Surface Degradation of Li- and Mn-Rich Layered Oxides in Variation of the Li₂MnO₃Content

Teufl

Strehle

Müller³

et al. 2018

J. Electrochem. Soc.

157

View full text Add to dashboard Cite

show abstract

“…Oxygen redox activity has been proposed as a possible source of the excess lithium extraction capacity in Li-excess-TM-oxide intercalation materials, such as Li 2 MnO 3 -LiMO 2 , [16,17] [4,18,19] , Co doped Li 2 O [20] Li x Ni 2-4x/3 Sb x/3 O 2 [21] and Li-Nb-M-O [22,23] systems. Such…”

Section: Introductionmentioning

confidence: 99%

“…However, the aforementioned materials exhibit a surplus capacity that cannot be explained by the TM redox couples but is commonly attributed to oxygen redox activity. [4,[16][17][18][19][20]22] Reversible charge transfer to oxygen in bulk electrode materials may become an exciting new pathway for energy storage with increased energy density.…”

Section: Introductionmentioning

confidence: 99%

Calibrating transition-metal energy levels and oxygen bands in first-principles calculations: Accurate prediction of redox potentials and charge transfer in lithium transition-metal oxides

2015

View full text Add to dashboard Cite

Transition metal (TM) oxides play an increasingly important role in technology today including applications such as catalysis, solar energy harvesting, and energy storage. In many of these applications, the details of their electronic structure near the Fermi level are critically important for their properties. We propose a first-principles based computational methodology for the accurate prediction of oxygen charge transfer in TM oxides and lithium TM (Li-TM) oxides. To obtain accurate electronic structures, the Heyd-Scuseria-Ernzerhof (HSE06) hybrid functional is adopted and the amount of exact Hartree-Fock exchange (mixing parameter) is adjusted to reproduce reference band gaps.We show that the HSE06 functional with optimal mixing parameter yields not only improved electronic densities of states but also better energetics (Li-intercalation voltages) for LiCoO 2 and LiNiO 2 as compared to GGA, GGA+U and standard HSE06.We find that the optimal mixing parameters for TM oxides are system-specific and correlate with the covalency (ionicity) of the TM species. Strong covalent (ionic) nature of TM-O bonding leads to lower (higher) optimal mixing parameters. We find that optimized HSE06 functionals predict stronger hybridization of the Co 3d and O 2p orbitals than GGA, resulting in a greater contribution from oxygen states to charge compensation upon delithiation in LiCoO 2 . We also find that the band gaps of Li-TM oxides increase linearly with the mixing parameter, enabling the straightforward determination of optimal mixing parameters based on GGA (α = 0.0) and HSE06 (α = 0.25) calculations. Our results also show that G 0 W 0 @GGA+U band gaps of TM oxides (MO, M = Mn, Co, Ni) and LiCoO 2 agree well with experimental references, suggesting that G 0 W 0 calculations can be used as a reference for the calibration of the mixing parameter in case no experimental band gap has been reported. 3

show abstract

“…19,22,23 However, to obtain such a capacity, these materials must be cycled over a wide potential range of 2.5-4.6 V (vs. Li + /Li), which may be challenging for the current carbonate-based electrolytes. Major issues such as large irreversible capacity (IRC), 19,33,34 voltage fade upon cycling 22,[35][36][37][38][39][40] and poor rate capability 22,41,42 have hindered the application of these materials. * Electrochemical Society Student Member.…”

mentioning

confidence: 99%

Study of the Failure Mechanisms of LiNi_0.8Mn_0.1Co_0.1O₂Cathode Material for Lithium Ion Batteries

Downie

et al. 2015

J. Electrochem. Soc.

442

372

View full text Add to dashboard Cite

LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) can deliver a high capacity of ∼200 mAh/g with an average discharge potential of ∼3.8 V (vs. Li + /Li), making it a promising positive electrode material for high energy density lithium ion batteries. However, electrochemical tests from half cells and full cells show poor cycling performance when charged to potentials above 4.2 V. The calendar and cycle lifetimes of cells are affected by the structural stability of the active electrode materials as well as the parasitic reactions that occur in lithium ion batteries. In order to explore the major failure mechanisms of the material, half cells (coin cells) with control electrolyte and full cells (pouch cells) with control electrolyte and with selected electrolyte additives were tested over four different potential ranges. Isothermal microcalorimetry was used to explore the parasitic reactions and their potential dependence. In-situ and ex-situ X-ray diffraction and scanning electron microscopy were used to investigate the structural and morphological degradation of the materials over cycling. It was found that the dramatic c-axis change of the active material during charge and discharge may not be the major problem for cells that are cycled to higher potentials. The parasitic reactions that arise from the interactions between the electrolyte and the highly reactive delithiated cathode surface at high potentials are suggested as the main reason for the failure of cells cycled above 4.2 V. It should be possible to further improve the performance of NMC811 at high potentials by modifying the cathode surface and/or identifying and using electrolyte blends which reduce parasitic reactions. High energy density lithium ion batteries (LIBs) that are cheaper, safer, and with longer lifetimes need to be developed in order to meet the increasing demand for applications such as electric vehicles and large scale stationary energy storage. The energy density of LIBs can be increased by increasing the specific capacity and average potential of the cells. The calendar and cycle lifetimes of cells are affected by the structural stability of the active electrode materials as well as the parasitic reactions that occur in lithium ion batteries. The degree of lithium utilization of LiCoO 2 is limited to ∼70% in order avoid the O3 -H1-3 -O1 phase transformation when charged above 4.45 V.1 Parasitic reactions such as electrolyte oxidation at the cathode-electrolyte interface can ultimately cause cell failure.2-5 The rate of the parasitic reactions is related to both the catalytic role of the cathode surface which depends on its composition and surface area, 3,6 as well as on the stability of the electrolyte.2-5 Methods such as the use of electrolyte additives 7-11 and core-shell positive electrode materials [12][13][14] have been developed and studied to reduce the rate and extent of parasitic reactions, and hence increase capacity retention and lifetime of high-voltage Li-ion cells. The layered lithium Ni-Mn-Co oxides Li 1+x (Ni y Mn z Co (1-y-z) ) 1...

show abstract

Different oxygen redox participation for bulk and surface: A possible global explanation for the cycling mechanism of Li1.20Mn0.54Co0.13Ni0.13O2

Cited by 299 publications

References 31 publications

Oxygen Release and Surface Degradation of Li- and Mn-Rich Layered Oxides in Variation of the Li₂MnO₃Content

Oxygen Release and Surface Degradation of Li- and Mn-Rich Layered Oxides in Variation of the Li₂MnO₃Content

Calibrating transition-metal energy levels and oxygen bands in first-principles calculations: Accurate prediction of redox potentials and charge transfer in lithium transition-metal oxides

Study of the Failure Mechanisms of LiNi_0.8Mn_0.1Co_0.1O₂Cathode Material for Lithium Ion Batteries

Contact Info

Product

Resources

About

Different oxygen redox participation for bulk and surface: A possible global explanation for the cycling mechanism of Li1.20Mn0.54Co0.13Ni0.13O2

Cited by 299 publications

References 31 publications

Oxygen Release and Surface Degradation of Li- and Mn-Rich Layered Oxides in Variation of the Li2MnO3Content

Oxygen Release and Surface Degradation of Li- and Mn-Rich Layered Oxides in Variation of the Li2MnO3Content

Calibrating transition-metal energy levels and oxygen bands in first-principles calculations: Accurate prediction of redox potentials and charge transfer in lithium transition-metal oxides

Study of the Failure Mechanisms of LiNi0.8Mn0.1Co0.1O2Cathode Material for Lithium Ion Batteries

Contact Info

Product

Resources

About

Oxygen Release and Surface Degradation of Li- and Mn-Rich Layered Oxides in Variation of the Li₂MnO₃Content

Oxygen Release and Surface Degradation of Li- and Mn-Rich Layered Oxides in Variation of the Li₂MnO₃Content

Study of the Failure Mechanisms of LiNi_0.8Mn_0.1Co_0.1O₂Cathode Material for Lithium Ion Batteries