Altering Mechanical Properties to Improve Electrode Contacts by Organic Modification of Silica-Based Ionogel Electrolytes for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are a possible candidate to create safe, sustainable, and cost-effective batteries. Solid sodium-ion conducting organically modified ionogel electrolytes are investigated. Silica-based ionogels typically consist of an ionic liquid electrolyte (ILE) confined within a silica matrix and possess high thermal stability, good ionic conductivity, safety, and good electrochemical stability. However, they readily deteriorate when stress is applied, decreasing the electrolyte's and battery's overall performance. The mechanical characteristics of silica can be improved using organic moieties, creating Ormosils®. Silica-based ionogels with phenyl-modified silanes improve the mechanical characteristics by a reduction of their Young's modulus (from 29 to 6 MPa). This is beneficial to the charge-transfer resistance, which decreases after implementing the electrolyte in half cells, demonstrating the improved interfacial contact. Most importantly, the phenyl groups change the interacting species at the silica interface. Cationic imidazolium species pi-stacked to the phenyl groups of the silica matrix, pushing the anions to the bulk of the ILE, which affects the ionic conductivity and electrochemical stability, and might affect the quality of the SEI in half cells. In essence, the work at hand can be used as a directory to improve mechanical characteristics and modify and control functional properties of ionogel electrolytes.

Superconcentration Strategy Allows Sodium Metal Compatibility in Deep Eutectic Solvents for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are a more sustainable alternative to lithium-ion batteries (LIBs) considering the abundance, global distribution, and low cost of sodium. However, their economic impact remains small compared to LIBs, owing in part to the lag in materials development where significant improvements in energy density and safety remain to be realized. Deep eutectic solvents (DESs) show promise as alternatives to conventional electrolytes in SIBs because of their nonflammable nature. However, their practical application has thus far been hindered by their limited electrochemical stability window. In particular, DESs based on N-methylacetamide have thus far been reported not to be stable with sodium metal. In contrast, this work reports a superconcentration strategy where sodium-ion conducting DESs, based on the dissolution of NaFSI in N-methylacetamide, are simultaneously stable with sodium metal and Prussian blue as state-of-the-art positive electrode material. At 60 °C, the nonflammable DES outperforms a conventional liquid electrolyte in terms of rate performance and capacity retention. Therefore, these novel DES compositions pave the way for the use of DESs in practical applications with an improved safety and sustainability.

Polymeric Backbone Eutectogel Electrolytes for High-Energy Lithium-Ion Batteries.

This work introduces a polymeric backbone eutectogel (P-ETG) hybrid solid-state electrolyte with an N-isopropylacrylamide (NIPAM) backbone for high-energy lithium-ion batteries (LIBs). The NIPAM-based P-ETG is (electro)chemically compatible with commercially relevant positive electrode materials such as the nickel-rich layered oxide LiNi0.6Mn0.2Co0.2O2 (NMC622). The chemical compatibility was demonstrated through (physico)chemical characterization methods. The nonexistence (within detection limits) of interfacial reactions between the electrolyte and the positive electrode, the unchanged bulk crystallographic composition, and the absence of transition metal ions leaching from the positive electrode in contact with the electrolyte were demonstrated by Fourier transform infrared spectroscopy, powder X-ray diffraction, and elemental analysis, respectively. Moreover, the NIPAM-based P-ETG demonstrates a wide electrochemical stability window (1.5-5.0 V vs Li+/Li) and a reasonably high ionic conductivity at room temperature (0.82 mS cm-1). The electrochemical compatibility of a high-potential NMC622-containing positive electrode and the P-ETG is further demonstrated in Li|P-ETG|NMC622 cells, which deliver a discharge capacity of 134, 110, and 97 mAh g-1 at C/5, C/2, and 1C, respectively, after 90 cycles. The Coulombic efficiency is >95% at C/5, C/2, and 1C. Hence, gaining scientific insights into the compatibility of the electrolytes with positive electrode materials that are relevant to the commercial market, like NMC622, is important because this requires going beyond the electrolyte design itself, which is essential to their practical applications.

Solution-gel-based surface modification of LiNi0.5Mn1.5O4-δ with amorphous Li-Ti-O coating.

LNMO (LiNi0.5Mn1.5O4-δ) is a high-energy density positive electrode material for lithium ion batteries. Unfortunately, it suffers from capacity loss and impedance rise during cycling due to electrolyte oxidation and electrode/electrolyte interface instabilities at high operating voltages. Here, a solution-gel synthesis route was used to coat 0.5-2.5 µm LNMO particles with amorphous Li-Ti-O (LTO) for improved Li conduction, surface structural stability and cyclability. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) analysis coupled with energy dispersive X-ray (EDX) showed Ti-rich amorphous coatings/islands or Ti-rich spinel layers on many of the LTO-modified LNMO facets, with a thickness varying from about 1 to 10 nm. The surface modification in the form of amorphous islands was mostly possible on high-energy crystal facets. Physicochemical observations were used to propose a molecular mechanism for the surface modification, combining insights from metalorganic chemistry with the crystallographic properties of LNMO. The improvements in functional properties were investigated in half cells. The cell impedance increased faster for the bare LNMO compared to amorphous LTO modified LNMO, resulting in Rct values as high as 1247 Ω (after 1000 cycles) for bare LNMO, against 216 Ω for the modified material. At 10C, the modified material boosted a 15% increase in average discharge capacity. The improvements in electrochemical performance were attributed to the increase in electrochemically active surface area, as well as to improved HF-scavenging, resulting in the formation of protective byproducts, generating a more stable interface during prolonged cycling.