Journal ArticleDOI
Reversible anionic redox chemistry in high-capacity layered-oxide electrodes
Mariyappan Sathiya,Gwenaëlle Rousse,Kannadka Ramesha,C.P. Laisa,Hervé Vezin,Moulay Tahar Sougrati,Moulay Tahar Sougrati,Marie-Liesse Doublet,Dominique Foix,Danielle Gonbeau,Danielle Gonbeau,Wesley Walker,Annigere S. Prakash,M. Ben Hassine,M. Ben Hassine,Loic Dupont,Loic Dupont,Jean-Marie Tarascon,Jean-Marie Tarascon +18 more
TLDR
In this article, the reactivity of a class of high-capacity oxides with a single redox cation has been investigated and it has been shown that these oxides exhibit sustainable reversible capacities as high as 230 mAh/g−1 and good cycling behavior with no signs of voltage decay.Abstract:
Li-ion batteries have contributed to the commercial success of portable electronics and may soon dominate the electric transportation market provided that major scientific advances including new materials and concepts are developed. Classical positive electrodes for Li-ion technology operate mainly through an insertion-deinsertion redox process involving cationic species. However, this mechanism is insufficient to account for the high capacities exhibited by the new generation of Li-rich (Li1+xNiyCozMn(1−x−y−z)O2) layered oxides that present unusual Li reactivity. In an attempt to overcome both the inherent composition and the structural complexity of this class of oxides, we have designed structurally related Li2Ru1−ySnyO3 materials that have a single redox cation and exhibit sustainable reversible capacities as high as 230 mA h g−1. Moreover, they present good cycling behaviour with no signs of voltage decay and a small irreversible capacity. We also unambiguously show, on the basis of an arsenal of characterization techniques, that the reactivity of these high-capacity materials towards Li entails cumulative cationic (Mn+→M(n+1)+) and anionic (O2−→O22−) reversible redox processes, owing to the d-sp hybridization associated with a reductive coupling mechanism. Because Li2MO3 is a large family of compounds, this study opens the door to the exploration of a vast number of high-capacity materials.read more
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Journal ArticleDOI
Charging Mechanism of Li2MnO3
Niccoló Guerrini,Liyu Jin,Juan G. Lozano,Kun Luo,Adam Sobkowiak,Kazuki Tsuruta,Felix Massel,L.-C. Duda,Matthew R. Roberts,Peter G. Bruce +9 more
TL;DR: In this article, the authors demonstrate quantitatively that lithium extraction from Li2MnO3 is charge compensated by oxygen loss (O-loss) not oxidation of oxide ions that are retained within the st...
Journal ArticleDOI
Oxygen activity and peroxide formation as charge compensation mechanisms in Li2MnO3
Anika Marusczyk,Anika Marusczyk,Jan-Michael Albina,Thomas Hammerschmidt,Ralf Drautz,Thomas Eckl,Graeme Henkelman +6 more
TL;DR: In this paper, hole doping into the oxygen bands is the primary charge compensation mechanism in the first stage of delithiation, and there is an energetic driving force for peroxide formation with an optimal number of peroxide dimers that is predicted as a function of lithium concentration.
Journal ArticleDOI
The superior electrochemical performance of a Li-rich layered cathode material with Li-rich spinel Li4Mn5O12 and MgF2 double surface modifications
Wei Zhu,Zige Tai,Chengyong Shu,Shaokun Chong,Shengwu Guo,Lijie Ji,Yuanzhen Chen,Yongning Liu +7 more
TL;DR: Li et al. as discussed by the authors constructed Li-rich spinel Li4Mn5O12 and MgF2 by simple liquid-phase erosion and liquid phase deposition methods, respectively.
Journal ArticleDOI
Inhibition of oxygen dimerization by local symmetry tuning in Li-rich layered oxides for improved stability.
Fanghua Ning,Biao Li,Jin Song,Yuxuan Zuo,Huaifang Shang,Zimeng Zhao,Zhen Yu,Wangsheng Chu,Kun Zhang,Guang Feng,Xiayan Wang,Dingguo Xia +11 more
TL;DR: A new structural response mechanism inhibiting O–O dimerization for the oxygen redox reaction by tuning the local symmetry around the oxygen ions is proposed, enabling significantly enhanced cycling stability and negligible voltage decay.
Journal ArticleDOI
Anionic Redox Activity as a Key Factor in the Performance Degradation of NaFeO2 Cathodes for Sodium Ion Batteries
Dieky Susanto,Min Kyung Cho,Ghulam Ali,Jiyoung Kim,Hye Jung Chang,Hyung-Seok Kim,Kyung-Wan Nam,Kyung Yoon Chung +7 more
TL;DR: In this paper, the origin of the irreversible capacity of O3-type NaFeO2 charged to high voltage was investigated by analyzing the oxidation state of Fe and phase transition of layered NaFe O2 cathodes for sodium-i...
References
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Journal ArticleDOI
Generalized Gradient Approximation Made Simple
TL;DR: A simple derivation of a simple GGA is presented, in which all parameters (other than those in LSD) are fundamental constants, and only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked.
Journal ArticleDOI
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set.
Georg Kresse,Jürgen Furthmüller +1 more
TL;DR: An efficient scheme for calculating the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set is presented and the application of Pulay's DIIS method to the iterative diagonalization of large matrices will be discussed.
Journal ArticleDOI
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
TL;DR: The effective ionic radii of Shannon & Prewitt [Acta Cryst. (1969), B25, 925-945] are revised to include more unusual oxidation states and coordinations as mentioned in this paper.
Journal ArticleDOI
Issues and challenges facing rechargeable lithium batteries
TL;DR: A brief historical review of the development of lithium-based rechargeable batteries is presented, ongoing research strategies are highlighted, and the challenges that remain regarding the synthesis, characterization, electrochemical performance and safety of these systems are discussed.
Journal ArticleDOI
Building better batteries
TL;DR: Researchers must find a sustainable way of providing the power their modern lifestyles demand to ensure the continued existence of clean energy sources.