Role of the LiPF6 Salt for the Long Term Stability of Silicon Electrodes in Li Ion Batteries A Photoelectron Spectroscopy Study

cited By 83International audienceSilicon presents a very high theoretical capacity (3578 mAh/g) and appears as a promising candidate for the next generation of negative electrodes for Li-ion batteries. An important issue for the implementation of silicon is the understanding of the interfacial chemistry taking place during charge/discharge since it partly explains the capacity fading usually observed upon cycling. In this work, the mechanism for the evolution of the interfacial chemistry (reaction of surface oxide, Li-Si alloying process, and passivation layer formation) upon long-term cycling has been investigated by photoelectron spectroscopy (XPS or PES). A nondestructive depth resolved analysis was carried out by using both soft X-rays (100-800 eV) and hard X-rays (2000-7000 eV) from two different synchrotron facilities. The results are compared with those obtained with an in-house spectrometer (1486.6 eV). The important role played by the LiPF6 salt on the stability of the silicon electrode during cycling has been demonstrated in this study. A partially fluorinated species is formed upon cycling at the outermost surface of the silicon nanoparticles as a result of the reaction of the materials toward the electrolyte. We have shown that a similar species is also formed by simple contact between the electrolyte and the pristine electrode. The reactivity between the electrode and the electrolyte is investigated in this work. Finally, we also report in this work the evolution of the composition and covering of the SEI upon cycling as well as proof of the protective role of the SEI when the cell is at rest. © 2013 American Chemical Society

SEI Composition on Hard Carbon in Na-Ion Batteries After Long Cycling: Influence of Salts (NaPF 6 , NaTFSI) and Additives (FEC, DMCF)

International audienceA study of the Solid Electrolyte Interphase (SEI) on hard-carbon (HC) electrodes in sodium half-cells is presented. Electrochemical performances over > 100 cycles were compared with two different salts (NaPF6, NaTFSI) and two different electrolyte additives (FEC, DMCF) in a mixture of EC and DMC solvents. The best electrochemical performances were observed with NaPF6 salt in conjunction with 3% FEC. The DMCF additive had a detrimental effect in all electrolyte combinations. The chemical characterization of the SEI was carried out by X-ray Photoelectron Spectroscopy (XPS) and showed that the best electrochemical behavior was related to an SEI composition based on sodium ethylene dicarbonate and NaF, whereas poorer electrochemical performances were associated to either low NaF or high Na2CO3 content. The results reported herein provide an insight on the SEI chemistry on hard carbon electrodes in sodium cells after long-term cycling, as a complement to previous studies dealing with the first cycles

Decoupling Cationic-Anionic Redox Processes in a Model Li-Rich Cathode via Operando X-ray Absorption Spectroscopy

cited By 1International audienceThe demonstration of reversible anionic redox in Li-rich layered oxides has revitalized the search for higher energy battery cathodes. To advance the fundamentals of this promising mechanism, we investigate herein the cationic-anionic redox processes in Li2Ru0.75Sn0.25O3 - a model Li-rich layered cathode in which Ru (cationic) and O (anionic) are the only redox-active sites. We reveal its charge compensation mechanism and local structural evolutions by applying operando (and complementary ex situ) X-ray absorption spectroscopy (XAS). Among other local effects, the anionic-oxidation-driven distortion of the oxygen network around Ru atoms is thereby visualized. Oxidation of lattice oxygen is also directly proven via hard X-ray photoelectron spectroscopy (HAXPES). Furthermore, we demonstrate a spectroscopy-driven visualization of electrochemical reaction paths, which enabled us to neatly decouple the individual cationic-anionic dQ/dV contributions during cycling. We hence establish the redox and structural origins of all dQ/dV features and demonstrate the vital role of anionic redox in hysteresis and kinetics. These fundamental insights about Li-rich systems are crucial for improving the existing anionic-redox-based cathodes and evaluating the ones being discovered rapidly

XPS Investigation of Surface Reactivity of Electrode Materials: Effect of the Transition Metal

International audienceThe role of the transition metal nature and Al2O3 coating on the surface reactivity of LiCoO2 and LiNi1/3Mn1/3Co1/3O2 (NMC) materials were studied by coupling chemisorption of gaseous probes molecules and X-ray photoelectron (XPS) spectroscopy. The XPS analyses have put in evidence the low reactivity of the LiMO2 materials toward basic gaseous probe (NH3). The reactivity toward SO2 gaseous probe is much larger (roughly more than 10 times) and strongly influenced by the nature of metal. Only one adsorption mode (redox process producing adsorbed sulfate species) was observed at the LiCoO2 surface, while NMC materials exhibit sulfate and sulfite species at the surface. On the basis of XPS analysis of bare materials and previous theoretical work, we propose that the acidbase adsorption mode involving the Ni2+ cation is responsible for the sulfite species on the NMC surface. After Al2O3 coating, the surface reactivity was clearly decreasing for both LiCoO2 and NMC materials. In addition, for LiCoO2, the coating modifies the surface reactivity with the identification of both sulfate and sulfite species. This result is in line with a change in the adsorption mode from redox toward acidbase after Al/Co substitution. In the case of NMC materials, the coating induced a decrease of the sulfite species content at the surface. This phenomenon can be related to the cation mixing effect in the NMC

Manganese modified zeolite silicalite-1 as polysulphide sorbent in lithium sulphur batteries

cited By 11International audienceDischarge/charge process of classical lithium sulphur battery proceeds through intermediate polysulphides which are soluble in classical electrolyte systems. Due to concentration gradient soluble polysulphides easily diffuse/migrate out from cathode composite forming non-uniform distribution of the sulphur within cathode. Eventually polysulphides can be completely reduced on the metallic lithium anode. In this work we compare the sorption properties of manganese modified zeolite silicalite-1 (MnS-1) with a cathode composite containing SBA-15 additive and a cathode composite without additive. Careful analysis using XPS and FIB microscopy equipped with EDX show improved retention of polysulphide species within cathode composite in the case of MnS-1 zeolite as an additive. Interestingly, the amount of sulphur species detected by XPS on the metallic lithium is very similar regardless on cathode composite we use. Finally, similar cycling behaviour can be observed if MnS-1 zeolite is used as an interlayer between composite cathode and separator. © 2014 Elsevier B.V

Application of gel polymer electrolytes based on ionic liquids in lithium-sulfur batteries

International audienceIn this study, a gel polymer electrolyte (GPE) based on polymer ionic liquid (PIL) is used in a solvent-free and in a hybrid electrolyte configuration for Li-S batteries. Results obtained in the solvent-free configuration show a high discharge capacity in the first cycle and excellent coulombic efficiency during cycling. Capacity fading and polarization increase during cycling are explained based on the XPS and EIS measurements. The results of the present study are indicating that the increase of various internal resistance contributions and capacity fading are related with an accumulation of polysulfides in the GPE-PIL layer or/and on the surface of the lithium anode. Within a hybrid battery configuration, the thickness of the GPE-PIL layer is thinner, and the volume where polysulfides can be trapped is smaller. Such a configuration shows better cycling stability. The hybrid configuration outperforms cycling stability of the conventional configuration with a liquid electrolyte. This is explained by increased internal resistance in the convential configuration while the polarization in the first 100 cycles is constant in the hybrid configuration. Additionally, the hybrid configuration exhibits excellent C-rate performance. © 2016 The Electrochemical Society