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
Citations
More filters
Journal ArticleDOI
Operando X-ray Absorption Study of the Redox Processes Involved upon Cycling of the Li-Rich Layered Oxide Li1.20Mn0.54Co0.13Ni0.13O2 in Li Ion Batteries
Hideyuki Koga,Hideyuki Koga,Laurence Croguennec,Michel Ménétrier,P. Mannessiez,François Weill,Claude Delmas,S. Belin +7 more
TL;DR: In this paper, the results obtained especially at the Mn K-edge fully support the participation of oxygen in the reversible charge-discharge reaction of this Li and Mn-rich layered material as a redox center and not only with oxygen loss.
Journal ArticleDOI
High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions
Kehua Dai,Kehua Dai,Jinpeng Wu,Jinpeng Wu,Zengqing Zhuo,Zengqing Zhuo,Qinghao Li,Qinghao Li,Shawn Sallis,Shawn Sallis,Jing Mao,Guo Ai,Guo Ai,Chihang Sun,Zaiyuan Li,William E. Gent,William C. Chueh,William C. Chueh,Yi-De Chuang,Rong Zeng,Zhi-Xun Shen,Feng Pan,Shishen Yan,Louis F. J. Piper,Zahid Hussain,Gao Liu,Wanli Yang +26 more
TL;DR: In this paper, a mapping of resonant inelastic X-ray scattering (mRIXS) was used to quantitatively quantify the evolving redox states of both cations and anions in Na2/3Mg1/3mn2/ 3O2 and Li1.17Ni0.21Co0.08Mn0.54O2 systems.
Journal ArticleDOI
A General Method to Probe Oxygen Evolution Intermediates at Operating Conditions
Hua Bing Tao,Yinghua Xu,Xiang Huang,Jiazang Chen,Linjuan Pei,Junming Zhang,Jingguang G. Chen,Bin Liu +7 more
TL;DR: In this paper, a general method for operando probing OER intermediates under real working conditions was developed, which proved that the electrochemically generated oxygen intermediates of OER, e.g., OH*, are electrophiles, which could be probed by reaction with nucleophiles such as alcohol molecules.
Journal ArticleDOI
A High-Capacity O2-Type Li-Rich Cathode Material with a Single-Layer Li2MnO3 Superstructure
TL;DR: It is shown that an O2-type Li-rich material with a single-layer Li2 MnO3 superstructure can deliver an extraordinary reversible capacity of 400 mAh g-1 (energy density: ≈1360 Wh kg-1 ).
Journal ArticleDOI
Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen
Nika Mahne,Sara E. Renfrew,Sara E. Renfrew,Bryan D. McCloskey,Bryan D. McCloskey,Stefan Freunberger +5 more
TL;DR: It is shown that highly reactive singlet oxygen (1O2) forms upon oxidizing Li2CO3 in an aprotic electrolyte and therefore does not evolve as O2 and therefore underpin the importance of avoiding 1O2 in metal‐O2 batteries, and question the possibility of a reversible metal-O2/CO2 battery based on a carbonate discharge product.
References
More filters
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.