Silicon anode solid-state batteries Research on solid-state batteries has focused on lithium metal anodes. Alloy-based anodes have received less attention in part due to their lower specific capacity even though they should be safer. Tan et al . developed a slurry-based approach to create films from micrometer-scale silicon particles that can be used in anodes with carbon binders. When incorporated into solid-state batteries, they showed good performance across a range of temperatures and excellent cycle life in full cells. —MSL
MXenes are a family of two-dimensional (2D) transition metal carbides, nitrides, and carbonitrides with a general formula of M n+1 X n T x , in which two, three, or four atomic layers of a transition metal (M: Ti, Nb, V, Cr, Mo, Ta, etc.) are interleaved with layers of C and/or N (shown as X), and T x represents surface termination groups such as −OH, O, and −F. Here, we report the scalable synthesis and characterization of a MXene with five atomic layers of transition metals (Mo 4 VC 4 T x ), by synthesizing its Mo 4 VAlC 4 MAX phase precursor that contains no other MAX phase impurities. These phases display twinning at their central M layers which is not present in any other known MAX phases or MXenes. Transmission electron microscopy and X-ray diffraction were used to examine the structure of both phases. Energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and highresolution scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy were used to study the composition of these materials. Density functional theory calculations indicate that other five transition metal-layer MAX phases (M′ 4 M″AlC 4 ) may be possible, where M′ and M″ are two different transition metals. The predicted existence of additional Al-containing MAX phases suggests that more M 5 C 4 T x MXenes can be synthesized. Additionally, we characterized the optical, electronic, and thermal properties of Mo 4 VC 4 T x . This study demonstrates the existence of an additional subfamily of M 5 X 4 T x MXenes as well as a twinned structure, allowing for a wider range of 2D structures and compositions for more control over properties, which could lead to many different applications.
Two-dimensional (2D) transition-metal carbides and nitrides (MXenes) have attracted significant attention due to their electronic, electrochemical, chemical, and optical properties. However, understanding of their thermal stability is still lacking. To date, MXenes are synthesized via top-down wet chemical etching, which intrinsically results in surface terminations. Here, we provide detailed insight into the surface terminations of three carbide MXenes (Ti 3 C 2 T x , Mo 2 CT x , and Nb 2 CT x ) by performing thermal gravimetric analysis with mass spectrometry analysis (TA−MS) up to 1500 °C under a He atmosphere. This specific technique enables probing surface terminations including hydroxyl (−OH), oxy (O), and fluoride (−F) and intercalated species, such as salts and structural water. The MXene hydrophilicity depends on the type of etching (hydrofluoric acid concentration and/or mixed acid composition) and subsequent delamination conditions. We show that the amount of structural water in Ti 3 C 2 T x increases with decreasing O-containing surface terminations. The thermal stability of Ti 3 C 2 T x is improved by employing a low HF concentration or using a mixture of etchant acids, such as H 2 SO 4 /HF or HCl/HF instead of only HF, due to the reduced defect density. When tetramethylammonium hydroxide (TMAOH) is used for delamination, new N-containing species appear on the MXene surface. Moreover, free-standing films produced from Ti 3 C 2 T x etched with different HF concentrations and delaminated using TMAOH have similar TA−MS profiles, indicating that the post-treatment of Ti 3 C 2 T x controls its surface chemistry. The thermal stability of MXenes strongly depends on their chemical composition and structure; Ti 3 C 2 T x is more thermally stable than the fewer-atomic-layered Mo 2 CT x or Nb 2 CT x , and Mo 2 CT x is more/less thermally stable than Nb 2 CT x .
Rechargeable solid-state sodium-ion batteries (SSSBs) hold great promise for safer and more energy-dense energy storage. However, the poor electrochemical stability between current sulfide-based solid electrolytes and high-voltage oxide cathodes has limited their long-term cycling performance and practicality. Here, we report the discovery of the ion conductor Na3-xY1-xZrxCl6 (NYZC) that is both electrochemically stable (up to 3.8 V vs. Na/Na+) and chemically compatible with oxide cathodes. Its high ionic conductivity of 6.6 × 10−5 S cm−1 at ambient temperature, several orders of magnitude higher than oxide coatings, is attributed to abundant Na vacancies and cooperative MCl6 rotation, resulting in an extremely low interfacial impedance. A SSSB comprising a NaCrO2 + NYZC composite cathode, Na3PS4 electrolyte, and Na-Sn anode exhibits an exceptional first-cycle Coulombic efficiency of 97.1% at room temperature and can cycle over 1000 cycles with 89.3% capacity retention at 40 °C. These findings highlight the immense potential of halides for SSSB applications.
MXenes demonstrate high performance in energy storage. We report the synthesis and electrochemical characterization of a novel MXene, MoxV4−xC3.
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