The composition, morphology, and evolution of the solid electrolyte interphase (SEI) formed on hard carbon (HC) electrodes upon cycling in sodium-ion batteries are investigated. A microporous HC was prepared by pyrolysis of d-(+)-glucose at 1000°C followed by ball-milling. HC electrodes were galvanostatically cycled at room temperature in sodium-ion half-cells using an aprotic electrolyte of 1 m sodium bis(trifluoromethanesulfonyl)imide dissolved in propylene carbonate with 3 wt % fluoroethylene carbonate additive. The evolution of the elec-trode/electrolyte interface was studied by impedance spectroscopy upon cycling and ex situ by spectroscopy and microscopy. The irreversible capacity displayed by the HC electrodes in the first galvanostatic cycle is probably due to the accumulation of redox inactive Na x C phases and the precipitation of a porous, organic-inorganic hybrid SEI layer over the HC electrodes. This passivation film further evolves in morphology and composition upon cycling and stabilizes after approximately ten galvanostatic cycles at low current rates.[a] Dr.

Li-O2 batteries are currently one of the most advanced and challenging electrochemical systems with the potential to largely overcome the performances of any existing technology for energy storage and conversion. However, these optimistic expectations are frustrated by the still inadequate understanding of the fundamentals of the electrochemical/chemical reactions occurring at the cathode side, as well as within the electrolyte and at the three-phase interface. In this work, we illustrate the evolution of the morphology and composition of a carbonaceous cathode in the first discharge/charge in a Li-O2 cell with an ether-based electrolyte by X-ray photoemission spectroscopy, Fourier transform infrared spectroscopy, and transmission electron microscopy. Experiments have been carried out ex situ on electrodes recuperated from electrochemical cells stopped at various stages of galvanostatic discharge and charge. Apparently, a reversible accumulation and decomposition of organic and inorganic precipitates occurs upon discharge and charge, respectively. These precipitations and decompositions are likely driven by electrochemical and chemical parasitic processes due to the reactivity of the cathode carbonaceous matrix.

Potassium-ion (K-ion) batteries (KIBs) potentially offer numerous advantages over conventional lithium-ion batteries as a result of the high natural abundance of potassium and its lower positive charge density compared with lithium. This introduces the possibility of using K-ion in fast charging applications, in which cost effectiveness is also a major factor. Unlike in sodium-ion batteries, graphite can be used as an anode in K-ion cells, for which an extensive supply chain, electrode manufacturing infrastructure, and knowledge already exist. However, the performance of graphite anodes in K-ion cells does not meet expectations, with rapid capacity fading and poor first cycle irreversible capacities often reported. Here, we investigate the formation and composition of the solid electrolyte interphase (SEI) as well as K+ insertion in graphite anodes in KIBs. Through the use of energy-tuned synchrotron-based X-ray photoelectron spectroscopy, we make a detailed analysis at three probing depths up to ∼50 nm of graphite anodes cycled to various potentials on the first discharge–charge cycle. Extensive SEI formation from a KPF6/DEC/EC electrolyte system is found to occur at low potentials during the insertion of potassium ions into graphite. During the subsequent removal of potassium ions from the structure, the thick SEI is partially stripped from the electrode, demonstrating that the SEI layer is unstable and contributes to a significant proportion of the capacity upon both discharge and charge. With this in mind, further work is required to develop an electrolyte system with stable SEI layer formation on graphite in order to advance the KIB technology.

Na-O batteries are regarded as promising candidates for energy storage. They have higher energy efficiency, rate capability, and chemical reversibility than Li-O batteries; in addition, sodium is cheaper and more abundant compared to lithium. However, inconsistent observations and instability of discharge products have inhibited the understanding of the working mechanism of this technology. In this work, we have investigated a number of factors that influence the stability of the discharge products. By means of in operando powder X-ray diffraction study, the influence of oxygen, sodium anode, salt, solvent, and carbon cathode were investigated. The Na metal anode and an ether-based solvent are the main factors that lead to the instability and decomposition of NaO in the cell environment. This fundamental insight brings new information on the working mechanism of Na-O batteries.

The reaction thermodynamics of the 1,2-dimethoxyethane (DME), a model solvent molecule commonly used in electrolytes for Li-O rechargeable batteries, has been studied by first-principles methods to predict its degradation processes in highly oxidizing environments. In particular, the reactivity of DME towards the superoxide anion O in oxygen-poor or oxygen-rich environments is studied by density functional calculations. Solvation effects are considered by employing a self-consistent reaction field in a continuum solvation model. The degradation of DME occurs through competitive thermodynamically driven reaction paths that end with the formation of partially oxidized final products such as formaldehyde and methoxyethene in oxygen-poor environments and methyl oxalate, methyl formate, 1-formate methyl acetate, methoxy ethanoic methanoic anhydride, and ethylene glycol diformate in oxygen-rich environments. This chemical reactivity indirectly behaves as an electroactive parasitic process and therefore wastes part of the charge exchanged in Li-O cells upon discharge. This study is the first complete rationale to be reported about the degradation chemistry of DME due to direct interaction with O /O molecules. These findings pave the way for a rational development of new solvent molecules for Li-O electrolytes.

In this work we discuss the degradation chemistry on carbon-free electrodes of two ether based electrolytes for Li-O 2 batteries, i.e. tetraethylene glycol dimethyl ether (TEGDME) and dimethoxy ethane (DME) with lithium trifluoromethane sulfonate (LiTfO) as salt. To this aim we developed an all-metallic positive electrode by electrodeposition of a gold dendritic film on a nickel foam (Au@Ni). These carbon-free electro-catalytic electrodes have been used to investigate the degradation chemistry of the electrolytes in Li-O 2 cells by eliminating the parallel parasitic reactions due to the commonly used carbon electro-catalysts. In particular the composition and morphological evolutions of the Au@Ni electrodes after discharge and cycling have been characterized ex situ by Raman Spectroscopy, X-ray Photoemission Spectroscopy and Scanning Electron Microscopy. We also couple this experimental study with thermodynamic predictions about the onset degradation of the DME molecule based on density functional theory calculations. In summary in both DME/LiTfO and TEGDME/LiTfO electrolytes, the degradation involves the oxidation of the ether solvent to a mixture of carbonates and carboxylates/formate/oxalate. DME is apparently more strongly degraded compared to TEGDME whereas the LiTfO anion is highly stable. Calculations suggest the key role played by the singlet oxygen molecule as initiator of the degradation path.

Ball-milling of graphite results in graphene layer exfoliation and defect formation, leading to enhanced performance as a K-ion battery anode.

Herein, Zn plating–stripping onto metallic Zn using a couple of acetonitrile (AN)‐based electrolytes (0.5 m Zn(TFSI)2/AN and 0.5 m Zn(CF3SO3)2/AN) is studied. Both electrolytes show a reversible Zn plating/stripping over 1000 cycles at different applied current densities varying from 1.25 to 10 mA cm−2. The overpotentials of Zn plating–stripping over 500 cycles at constant current of 1.25 and 10 mA cm−2 are ±0.05 and ±0.2 V, respectively. X‐ray photoelectron spectroscopy analysis reveals that no decomposition product is formed on the Zn surface. The anodic stability of four different current collectors of aluminum foil (Al), carbon‐coated aluminum foil (C/Al), TiN‐coated titanium foil (TiN/Ti), and multiwalled carbon nanotube paper (MWCNT‐paper) is tested in both electrolytes. As a general trend, the current collectors have a higher anodic stability in Zn(TFSI)2/AN compared with Zn(CF3SO3)2/AN. The Al foil displays the highest anodic stability of ≈2.25 V versus Zn2+/Zn in Zn(TFSI)2/AN electrolyte. The TiN/Ti shows a comparable anodic stability with that of Al foil, but its anodic current density is higher than Al. The promising reversibility of the Zn plating/stripping combined with the anodic stability of Al and TiN/Ti current collectors paves the way for establishing highly reversible Zn‐ion batteries.