Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries

McCalla, Eric; Abakumov, Artem M.; Saubanère, Matthieu; Foix, Dominique; Berg, Erik J.; Rousse, Gwenaëlle; Doublet, Marie-Liesse; Gonbeau, Danielle; Novák, Petr; Tendeloo, Gustaaf Van; Dominko, Robert; Tarascon, J. M.

doi:10.1126/science.aac8260

Cited by 678 publications

(772 citation statements)

References 39 publications

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“…While some groups expect electrochemical activation of Li 2 MnO 3 to MnO 2 accompanied by bulk oxygen release, 11 more recent publications give strong evidence that anionic oxygen redox might serve for charge compensation at high delithiation. 26,[31][32][33] The specific role of oxygen release HE-NCM particularly during the first activation cycle will be analyzed and discussed later on.…”

Section: Resultsmentioning

confidence: 99%

“…This stabilization may explained by the compensation of repulsive forces between the transition metal layers at low lithium content, produced by the loss of lithium from the transition metal layer, thereby creating vacancies within the transition metal layers. These repulsive forces would furthermore be reduced by the reported reversible oxygen redox, 26,32,33 whereby it is conceivable that the creation of vacancies in the transition metal layer during the first activation cycle is responsible for enabling oxygen redox processes. 38 However, increasing the Li 2 MnO 3 content leads to an increased lithium occupation in the transition metal layer in the pristine material 58 that will be extracted during the first activation charge, leading to a destabilization of the surface at increasingly lower SOCs, as was discussed above.…”

Section: Discussionmentioning

confidence: 99%

“…10,30 In contradiction to the bulk oxygen release, the recent literature gives strong evidence that reversible anionic oxygen redox participation in the bulk material can serve for charge compensation and therefore explain the high reversible capacities within this class of materials. [31][32][33][34] Therefore, it is suggested that high degrees of delithiation and reversible oxygen redox trigger reversible and irreversible transition metal migration within the bulk material, leading to voltage fading and to the large charge/discharge voltage hysteresis due to the hindered lithium diffusion within the bulk material. 14,[35][36][37][38] In contradiction to the hypothesis of bulk oxygen release and bulk structural transformation, recent studies give clear evidence that the bulk structure is preserved, while a relatively small fraction of transition metals (about 10% over 100 cycles) 35 migrate reversibly and over extended charge/discharge cycling irreversibly between the transition metal and the lithium layers, leading to changes of the bulk material thermodynamics like the charge and discharge potentials as well as to the observed voltage fading.…”

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confidence: 99%

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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

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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...

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

mentioning

confidence: 99%

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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

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“…44 Figure 6 shows an atomic resolution image obtained by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) for the charged Li 0.5 IrO 3 sample. No migration of Ir ions is noted after charge, as expected from the high covalency of Ir ions with oxygen.…”

mentioning

confidence: 99%

Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries

Yabuuchi¹

2017

Chem. Lett.

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Research interest for a solid-state redox reaction of oxide ions (oxygen) is rapidly increasing for rechargeable battery applications. This article reviews the history and development of charge compensation mechanisms with oxide ions for electrode materials of batteries. Reversible and irreversible processes are observed after the oxidation of oxide ions, and it highly depends on the natures of chemical bonds between transition metals and oxide ions. Future possibility of high-energy lithium/sodium batteries with the oxide ion redox is also discussed.

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“…[7,8]. Recent work has confirmed electron holes on O atoms in Li-rich 3d transition metal oxides using X-ray spectroscopy, XANES and Raman spectroscopy [9].…”

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confidence: 99%

Using Advanced STEM Techniques to Unravel Key Issues in the Development of Next-Generation Nanostructures for Energy Storage

et al. 2017

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It is increasingly accepted that, in order to understand the relationship between structure and function of energy storage materials to achieve a much-needed step change in technology development, it is necessary to understand local structure. This is particularly important in the technologically relevant Lirich transition metal oxides (TMOs), in which the processes that currently inhibit their larger-scale utilization are inherently local. In this class of material, it is known that increasing lithium and manganese contents towards a composition of Li1+xM1-xO2 (M is usually Co, Ni, Mn or combinations) leads to much higher capacities [1]. However, these materials suffer from voltage decay on cycling [2], mostly related to structural rearrangement at the atomic scale during charge-discharge cycles. Trapping of metal cations in the interstitial tetrahedral sites or formation of other phases including spinel, rock-salt or Mn3O4-like structures have been reported [3,4]. Although there is a general agreement on the structure of the pristine structures [5], the nature, amount and location of different phases formed at various states of charge is still subject of intense debate.A key structural question in these materials is the origin of the extra capacity and it has been suggested that oxygen loss [6], due to a partial oxidation of the oxygen sublattice is responsible. [7,8]. Recent work has confirmed electron holes on O atoms in Li-rich 3d transition metal oxides using X-ray spectroscopy, XANES and Raman spectroscopy [9]. However, short range structural changes in charged materials still remain poorly understood and requires advanced microscopy to make further improvements in our understanding of these phenomena.The aim of this work is to show the potential of advanced STEM based techniques to study these materials including imaging the oxygen sublattice. We focus on the case of Li-rich TMOs nanoparticles for use as cathode materials in the next generation of Li-ion batteries. The Li-rich TMO was synthesized using a sol-gel method [10] and the resulting nanoparticles had typical sizes of less than 120 nm. We used aberration-corrected ADF/ABF-STEM combined with multiframe acquisition methods [11] to correct for scan distortions and drift (see an example in Figure 1). This approach provided images with enough quality to monitor the oxygen sublattice for several different compositions.In addition, the feasibility of using electron ptychography to understand the structure of these oxides was evaluated. This technique recovers quantitative phase data simultaneously with incoherent signals, thus allowing us to image structures that contain light (lithium or sodium) and heavy elements (transition metals) concurrently [12]. Crucially, this method can be performed under extremely low electron doses, which drastically minimises beam damage. Therefore, it enables direct imaging of the atomic structure of pristine and charged samples and the monitoring of structural changes while minimising phase transformations induced by the ...

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Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries

Cited by 678 publications

References 39 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

Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries

Using Advanced STEM Techniques to Unravel Key Issues in the Development of Next-Generation Nanostructures for Energy Storage

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Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries

Cited by 678 publications

References 39 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

Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries

Using Advanced STEM Techniques to Unravel Key Issues in the Development of Next-Generation Nanostructures for Energy Storage

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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