Titanium Niobium Oxide Ti2 Nb10 O29 /Carbon Hybrid Electrodes Derived by Mechanochemically Synthesized Carbide for High-Performance Lithium-Ion Batteries.

This work introduces the facile and scalable two-step synthesis of Ti2 Nb10 O29 (TNO)/carbon hybrid material as a promising anode for lithium-ion batteries (LIBs). The first step consisted of a mechanically induced self-sustaining reaction via ball-milling at room temperature to produce titanium niobium carbide with a Ti and Nb stoichiometric ratio of 1 to 5. The second step involved the oxidation of as-synthesized titanium niobium carbide to produce TNO. Synthetic air yielded fully oxidized TNO, while annealing in CO2 resulted in TNO/carbon hybrids. The electrochemical performance for the hybrid and non-hybrid electrodes was surveyed in a narrow potential window (1.0-2.5 V vs. Li/Li+ ) and a large potential window (0.05-2.5 V vs. Li/Li+ ). The best hybrid material displayed a specific capacity of 350 mAh g-1 at a rate of 0.01 A g-1 (144 mAh g-1 at 1 A g-1 ) in the large potential window regime. The electrochemical performance of hybrid materials was superior compared to non-hybrid materials for operation within the large potential window. Due to the advantage of carbon in hybrid material, the rate handling was faster than that of the non-hybrid one. The hybrid materials displayed robust cycling stability and maintained ca. 70 % of their initial capacities after 500 cycles. In contrast, only ca. 26 % of the initial capacity was maintained after the first 40 cycles for non-hybrid materials. We also applied our hybrid material as an anode in a full-cell lithium-ion battery by coupling it with commercial LiMn2 O4 .

Ionic liquid-based synthesis of MXene.

MAX phases are etched using an ionic liquid-water mixture to produce titanium carbide MXenes. The process avoids the use of any acid. Hydrolysis of the fluorine-containing ionic liquid leads to the selective removal of Al, while the ionic liquid is intercalated in-between the transition metal carbide layers.

MXene/Activated-Carbon Hybrid Capacitive Deionization for Permselective Ion Removal at Low and High Salinity.

Two-dimensional, layered transition metal carbides (MXenes) are an intriguing class of intercalation-type electrodes for electrochemical applications. The ability for preferred counterion uptake qualifies MXenes as an attractive material for electrochemical desalination. Our work explores Ti3C2Tx-MXene paired with activated carbon in such a way that both electrodes operate in an optimized potential range. This is accomplished by electrode mass balancing and control over the cell voltage. Thereby, we enable effective remediation of saline media with low (brackish) and high (seawater-like) ionic strength by using 20 and 600 mM aqueous NaCl solutions. It is shown that MXene/activated-carbon asymmetric cell design capitalizes on the permselective behavior of MXene in sodium removal, which in turn forces carbon to mirror the same behavior in the removal of chloride ions. This has minimized the notorious co-ion desorption of carbon in highly saline media (600 mM NaCl) and boosted the charge efficiency from 4% in a symmetric activated-carbon/activated-carbon cell to 85% in a membrane-less asymmetric MXene/activated-carbon cell. Stable electrochemical performance for up to 100 cycles is demonstrated, yielding average desalination capacities of 8 and 12 mg/g, respectively, for membrane-less MXene/activated-carbon cells in NaCl solutions of 600 mM (seawater-level) and 20 mM (brackish-water-level). In the case of the 20 mM NaCl solutions, surprising charge efficiency values of over 100% have been obtained, which is attributed to the role of MXene interlayer surface charges.

In Situ Tracking of Partial Sodium Desolvation of Materials with Capacitive, Pseudocapacitive, and Battery-like Charge/Discharge Behavior in Aqueous Electrolytes.

Aqueous electrolytes can be used for electrical double-layer capacitors, pseudocapacitors, and intercalation-type batteries. These technologies may employ different electrode materials, most importantly high-surface-area nanoporous carbon, two-dimensional materials, and metal oxides. All of these materials also find more and more applications in electrochemical desalination devices. During the electrochemical operation of such electrode materials, charge storage and ion immobilization are accomplished by non-Faradaic ion electrosorption, Faradaic ion intercalation at specific crystallographic sites, or ion insertion between layers of two-dimensional materials. These processes may or may not be associated with a (partial) loss of the aqueous solvation shell around the ions. Our work showcases the electrochemical quartz crystal microbalance as an excellent tool for quantifying the change in effective solvation. We chose sodium as an important cation for energy storage materials (sodium-based aqueous electrolytes) and electrochemical desalination (saline media). Our data show that a major amount of water uptake occurs during ion electrosorption in nanoporous carbon, while battery-like ion insertion between layers of titanium disulfide is associated with an 80% loss of the initially present solvation molecules. Sodiation of MXene is accomplished by a loss of 90% of the number of solvent molecules, but nanoconfined water in-between the MXene layers may compensate for this large degree of desolvation. In the case of sodium manganese oxide, we were able to demonstrate the full loss of the solvation shell.