Chemical Prelithiated 3D Lithiophilic/-Phobic Interlayer Enables Long-Term Li Plating/Stripping.

The up-to-date lifespan of zero-excess lithium (Li) metal batteries is limited to a few dozen cycles due to irreversible Li-ion loss caused by interfacial reactions during cycling. Herein, a chemical prelithiated composite interlayer, made of lithiophilic silver (Ag) and lithiophobic copper (Cu) in a 3D porous carbon fiber matrix, is applied on a planar Cu current collector to regulate Li plating and stripping and prevent undesired reactions. The Li-rich surface coating of lithium oxide (Li2O), lithium carboxylate (RCO2Li), lithium carbonates (ROCO2Li), and lithium hydride (LiH) is formed by soaking and directly heating the interlayer in n-butyllithium hexane solution. Although only a thin coating of ∼10 nm is created, it effectively regulates the ionic and electronic conductivity of the interlayer via these surface compounds and reduces defect sites by reactions of n-butyllithium with heteroatoms in the carbon fibers during formation. The spontaneously formed lithiophilic-lithiophobic gradient across individual carbon fiber provides homogeneous Li-ion deposition, preventing concentrated Li deposition. The porous structure of the composite interlayer eliminates the built-in stress upon Li deposition, and the anisotropically distributed carbon fibers enable uniform charge compensation. These features synergistically minimize the side reactions and compensate for Li-ion loss while cycling. The prepared zero-excess Li metal batteries could be cycled 300 times at 1.17 C with negligible capacity fading.

Unraveling Propylene Oxide Formation in Alkali Metal Batteries.

The increasing need for electrochemical energy storage drives the development of post-lithium battery systems. Among the most promising new battery types are sodium-based battery systems. However, like its lithium predecessor, sodium batteries suffer from various issues like parasitic side reactions, which lead to a loss of active sodium inventory, thus reducing the capacity over time. Some problems in sodium batteries arise from an unstable solid electrolyte interphase (SEI) reducing its protective power e. g., due to increased solubility of SEI components in sodium battery systems. While it is known that the electrolyte affects the SEI structure, the exact formation mechanism of the SEI is not yet fully understood. In this study, we follow the initial SEI formation on a piece of sodium metal submerged in propylene carbonate with and without the electrolyte salt sodium perchlorate. We combine X-ray photoelectron spectroscopy, gas chromatography, and density functional theory to unravel the sudden emergence of propylene oxide after adding sodium perchlorate to the electrolyte solvent. We identify the formation of a sodium chloride layer as a crucial step in forming propylene oxide by enabling precursors formed from propylene carbonate on the sodium metal surface to undergo a ring-closing reaction. Based on our combined theoretical and experimental approach, we identify changes in the electrolyte decomposition process, propose a reaction mechanism to form propylene oxide and discuss alternatives based on known synthesis routes.

Styrene-Based Poly(ethylene oxide) Side-Chain Block Copolymers as Solid Polymer Electrolytes for High-Voltage Lithium-Metal Batteries.

Herein, we report the design of styrene-based poly(ethylene oxide) (PEO) side-chain block copolymers featuring a microphase separation and their application as solid polymer electrolytes in high-voltage lithium-metal batteries. A straightforward synthesis was established, overcoming typical drawbacks of PEO block copolymers prepared by anionic polymerization or ester-based PEO side-chain copolymers. Both the PEO side-chain length and the LiTFSI content were varied, and the underlying relationships were elucidated in view of polymer compositions with high ionic conductivity. Subsequently, a selected composition was subjected to further analyses, including phase-separated morphology, providing not only excellent self-standing films with intrinsic mechanical stability but also the ability to suppress lithium dendrite growth as well as good flexibility, wettability, and good contacts with the electrodes. Furthermore, good thermal and electrochemical stability was demonstrated. To do so, linear sweep and cyclic voltammetry, lithium plating/stripping tests, and galvanostatic overcharging using high-voltage cathodes were conducted, demonstrating stable lithium-metal interfaces and a high oxidative stability of around 4.75 V. Consequently, cycling of Li||NMC622 cells did not exhibit commonly observed rapid cell failure or voltage noise associated with PEO-based electrolytes in Li||NMC622 cells, attributed to the high mechanical stability. A comprehensive view is provided, highlighting that the combination of PEO and high-voltage cathodes is not impossible per se.

A Robust, Water-Based, Functional Binder Framework for High-Energy Lithium-Sulfur Batteries.

We report here a water-based functional binder framework for the lithium-sulfur battery systems, based on the general combination of a polyether and an amide-containing polymer. These binders are applied to positive electrodes optimised towards high-energy electrochemical performance based only on commercially available materials. Electrodes with up to 4 mAh cm-2 capacity and 97-98 % coulombic efficiency are achievable in electrodes with a 65 % total sulfur content and a poly(ethylene oxide):poly(vinylpyrrolidone) (PEO:PVP) binder system. Exchange of either binder component for a different polymer with similar functionality preserves the high capacity and coulombic efficiency. The improvement in coulombic efficiency from the inclusion of the coordinating amide group was also observed in electrodes where pyrrolidone moieties were covalently grafted to the carbon black, indicating the role of this functionality in facilitating polysulfide adsorption to the electrode surface. The mechanical properties of the electrodes appear not to significantly influence sulfur utilisation or coulombic efficiency in the short term but rather determine retention of these properties over extended cycling. These results demonstrate the robustness of this very straightforward approach, as well as the considerable scope for designing binder materials with targeted properties.

Surface Layer Evolution on Graphite During Electrochemical Sodium-tetraglyme Co-intercalation.

One obstacle in sodium ion batteries is the lack of suitable anode materials. As recently shown, the most common anode material of the state of the art lithium ion batteries, graphite, can be used for sodium ion storage as well, if ether-based electrolyte solvents are used. These solvents cointercalate with the sodium ions leading to the highly reversible formation of ternary graphite intercalation compounds (t-GIC). In order for the solvent cointercalation to work efficiently, it is expected that only a very thin surface layer forms during electrochemical cycling. In this article, we therefore present the first dedicated study of the surface layer evolution on t-GICs using soft X-ray photoelectron spectroscopy. This technique with its inherent high surface sensitivity and low probing depth is an ideal tool to study the underlying interfacial reactions during the sodiation and desodiation of graphite. In this report, we apply this approach to graphite composite electrodes cycled in Na half cells with a 1 M sodium bis(fluorosulfonyl)imide/tetraethylene glycol dimethyl ether (NaFSI/TEG-DME) electrolyte. We have found a surface layer on the cycled electrodes, mainly composed of salt decomposition products and hydrocarbons, in line with irreversible capacity losses observed in the electrochemical cycling. Although this surface layer does not seem to block cointercalation completely, it seems to affect its efficiency resulting in a low Coulombic efficiency of the studied battery system.

A stable graphite negative electrode for the lithium-sulfur battery.

Efficient, reversible lithium intercalation into graphite in ether-based electrolytes is enabled through a protective electrode binder, polyacrylic acid sodium salt (PAA-Na). In turn, this enables the creation of a stable "lithium-ion-sulfur" cell, using a lithiated graphite negative electrode with a sulfur positive electrode, using the common DME:DOL solvent system suited to the electrochemistry of the lithium-sulfur battery. Graphite-sulfur lithium-ion cells show average coulombic efficiencies of ∼99.5%, compared with <95% for lithium-sulfur cells, and significantly better capacity retention, taking into account cell balancing considerations. The high efficiency derives from the considerably better interfacial stability of the graphite electrode, which suppresses the polysulfide redox shuttle and self-discharge.

Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend.

This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li(+) coordination and transportation were studied in the ternary electrolyte system, i.e., PEO16LiTFSI⋅1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generated significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.

Why PEO as a binder or polymer coating increases capacity in the Li-S system.

PEO, used either as a binder or a polymer coating, and PEGDME, used as an electrolyte additive, are shown to increase the reversible capacity of Li-S cells. The effect, in all three cases, is the same: an improved solvent system for the electrochemistry of sulfur species and suppression of cathode passivation on discharge. This constitutes a novel interpretation of the mechanistic behaviour of polyethers in the Li-S system, and sheds new light upon several previous studies.