Anion Redox in an Amorphous Titanium Polysulfide.

Amorphous transition-metal polysulfides are promising positive electrode materials for next-generation rechargeable lithium-ion batteries because of their high theoretical capacities. In this study, sulfur anion redox during lithiation of amorphous TiS4 (a-TiS4) was investigated by using experimental and theoretical methods. It was found that a-TiS4 has a variety of sulfur valence states such as S2-, S-, and Sδ-. The S2- species became the main component in the Li4TiS4 composition, indicating that sulfur is a redox-active element up to this composition. The simulated a-TiS4 structure changed gradually by lithium accommodation to form a-Li4TiS4: S-S bonds in the disulfide units and polysulfide chains were broken. Bader charge analysis suggested that the average S valency decreased drastically. Moreover, deep lithiation of a-TiS4 provided a conversion reaction to metallic Ti and Li2S, with a high practical capacity of ∼1000 mAh g-1 when a lower cutoff voltage was applied.

[1]  H. Sakaebe,et al.  Reversible lithium insertion and conversion process of amorphous VS4 revealed by operando electrochemical NMR spectroscopy , 2022, Solid State Ionics.

[2]  H. Sakaebe,et al.  Improvement of Electrochemical Property of VS4 Electrode Material by Amorphization via Mechanical Milling Process , 2021, Electrochemistry.

[3]  C. Delmas,et al.  Lithium-rich layered titanium sulfides: Cobalt- and Nickel-free high capacity cathode materials for lithium-ion batteries , 2020 .

[4]  J. Tarascon,et al.  Publisher Correction: Exploring the bottlenecks of anionic redox in Li-rich layered sulfides , 2019, Nature Energy.

[5]  H. Sakaebe,et al.  Structural and dynamic behavior of lithium iron polysulfide Li 8 FeS 5 during charge–discharge cycling , 2018, Journal of Power Sources.

[6]  M. N. Kozlova,et al.  Anionic Redox Chemistry in Polysulfide Electrode Materials for Rechargeable Batteries. , 2017, ChemSusChem.

[7]  Mianqi Xue,et al.  Unique Reversible Conversion-Type Mechanism Enhanced Cathode Performance in Amorphous Molybdenum Polysulfide. , 2017, ACS applied materials & interfaces.

[8]  H. Sakaebe,et al.  Amorphous Metal Polysulfides: Electrode Materials with Unique Insertion/Extraction Reactions. , 2017, Journal of the American Chemical Society.

[9]  H. Sakaebe,et al.  Development of Li2TiS3–Li3NbS4 by a mechanochemical process , 2017 .

[10]  B. Dunn,et al.  Molybdenum polysulfide chalcogels as high-capacity, anion-redox-driven electrode materials for Li-ion batteries , 2016 .

[11]  Y. Orikasa,et al.  Structure analyses using X-ray photoelectron spectroscopy and X-ray absorption near edge structure for amorphous MS 3 (M: Ti, Mo) electrodes in all-solid-state lithium batteries , 2016 .

[12]  S. Jadkar,et al.  Temperature-Dependent Raman Spectroscopy of Titanium Trisulfide (TiS3) Nanoribbons and Nanosheets. , 2015, ACS applied materials & interfaces.

[13]  Jaephil Cho,et al.  Multiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfide. , 2015, Journal of the American Chemical Society.

[14]  M. N. Kozlova,et al.  Synthesis, crystal structure, and colloidal dispersions of vanadium tetrasulfide (VS4). , 2015, Chemistry.

[15]  H. Sakaebe,et al.  Composite positive electrode based on amorphous titanium polysulfide for application in all-solid-state lithium secondary batteries , 2014 .

[16]  H. Sakaebe,et al.  Preparation of Li2S-FeSx Composite Positive Electrode Materials and Their Electrochemical Properties with Pre-Cycling Treatments , 2014 .

[17]  H. Sakaebe,et al.  Rock-salt-type lithium metal sulphides as novel positive-electrode materials , 2014, Scientific Reports.

[18]  H. Sakaebe,et al.  Amorphous Niobium Sulfides as Novel Positive-Electrode Materials , 2014 .

[19]  Hajime Arai,et al.  In situ NMR observation of the lithium extraction/insertion from LiCoO2 cathode , 2013 .

[20]  H. Sakaebe,et al.  Amorphous TiS4 positive electrode for lithium–sulfur secondary batteries , 2013 .

[21]  Jaephil Cho,et al.  Synthesis and characterization of patronite form of vanadium sulfide on graphitic layer. , 2013, Journal of the American Chemical Society.

[22]  Guangyuan Zheng,et al.  Amphiphilic surface modification of hollow carbon nanofibers for improved cycle life of lithium sulfur batteries. , 2013, Nano letters.

[23]  Gérard Férey,et al.  Cathode composites for Li-S batteries via the use of oxygenated porous architectures. , 2011, Journal of the American Chemical Society.

[24]  I. Moudrakovski,et al.  Testing the sensitivity limits of ³³S NMR: an ultra-wideline study of elemental sulfur. , 2010, Journal of magnetic resonance.

[25]  Andrea R. Gerson,et al.  Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn , 2010 .

[26]  L. Nazar,et al.  Advances in Li–S batteries , 2010 .

[27]  C. Liang,et al.  Hierarchically Structured Sulfur/Carbon Nanocomposite Material for High-Energy Lithium Battery , 2009 .

[28]  L. Nazar,et al.  A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries. , 2009, Nature materials.

[29]  Artur F Izmaylov,et al.  Influence of the exchange screening parameter on the performance of screened hybrid functionals. , 2006, The Journal of chemical physics.

[30]  G. Henkelman,et al.  A fast and robust algorithm for Bader decomposition of charge density , 2006 .

[31]  H. Nesbitt,et al.  Polarized X-ray absorption spectroscopy and XPS of TiS , 2005 .

[32]  A. Benayad,et al.  XPS investigations of TiOySz amorphous thin films used as positive electrode in lithium microbatteries , 2005 .

[33]  Matt Probert,et al.  First principles methods using CASTEP , 2005 .

[34]  R. Bader,et al.  Atoms in molecules , 1990 .