The family of 2D transition metal carbides, carbonitrides and nitrides (collectively referred to as MXenes) has expanded rapidly since the discovery of Ti3C2 in 2011. The materials reported so far always have surface terminations, such as hydroxyl, oxygen or fluorine, which impart hydrophilicity to their surfaces. About 20 different MXenes have been synthesized, and the structures and properties of dozens more have been theoretically predicted. The availability of solid solutions, the control of surface terminations and a recent discovery of multi-transition-metal layered MXenes offer the potential for synthesis of many new structures. The versatile chemistry of MXenes allows the tuning of properties for applications including energy storage, electromagnetic interference shielding, reinforcement for composites, water purification, gas- and biosensors, lubrication, and photo-, electro- and chemical catalysis. Attractive electronic, optical, plasmonic and thermoelectric properties have also been shown. In this Review, we present the synthesis, structure and properties of MXenes, as well as their energy storage and related applications, and an outlook for future research. More than twenty 2D carbides, nitrides and carbonitrides of transition metals (MXenes) have been synthesized and studied, and dozens more predicted to exist. Highly electrically conductive MXenes show promise in electrical energy storage, electromagnetic interference shielding, electrocatalysis, plasmonics and other applications.

/pdf/2d-metal-carbides-and-nitrides-mxenes-for-energy-storage-4zg2z3wp7h.pdf

2D metal carbides and nitrides (MXenes) for energy storage

We developed two-step solution-phase reactions to form hybrid materials of Mn3O4 nanoparticles on reduced graphene oxide (RGO) sheets for lithium ion battery applications. Mn3O4 nanoparticles grown selectively on RGO sheets over free particle growth in solution allowed for the electrically insulating Mn3O4 nanoparticles wired up to a current collector through the underlying conducting graphene network. The Mn3O4 nanoparticles formed on RGO show a high specific capacity up to ~900mAh/g near its theoretical capacity with good rate capability and cycling stability, owing to the intimate interactions between the graphene substrates and the Mn3O4 nanoparticles grown atop. The Mn3O4/RGO hybrid could be a promising candidate material for high-capacity, low-cost, and environmentally friendly anode for lithium ion batteries. Our growth-on-graphene approach should offer a new technique for design and synthesis of battery electrodes based on highly insulating materials.

Mn3O4-Graphene Hybrid as a High Capacity Anode Material for Lithium Ion Batteries

Transition metal carbides and nitrides (MXenes), a family of two-dimensional (2D) inorganic compounds, are materials composed of a few atomic layers of transition metal carbides, nitrides, or carbonitrides. Ti3C2, the first 2D layered MXene, was isolated in 2011. This material, which is a layered bulk material analogous to graphite, was derived from its 3D phase, Ti3AlC2 MAX. Since then, material scientists have either determined or predicted the stable phases of >200 different MXenes based on combinations of various transition metals such as Ti, Mo, V, Cr, and their alloys with C and N. Extensive experimental and theoretical studies have shown their exciting potential for energy conversion and electrochemical storage. To this end, we comprehensively summarize the current advances in MXene research. We begin by reviewing the structure types and morphologies and their fabrication routes. The review then discusses the mechanical, electrical, optical, and electrochemical properties of MXenes. The focus then turns to their exciting potential in energy storage and conversion. Energy storage applications include electrodes in rechargeable lithium- and sodium-ion batteries, lithium-sulfur batteries, and supercapacitors. In terms of energy conversion, photocatalytic fuel production, such as hydrogen evolution from water splitting, and carbon dioxide reduction are presented. The potential of MXenes for the photocatalytic degradation of organic pollutants in water, such as dye waste, is also addressed, along with their promise as catalysts for ammonium synthesis from nitrogen. Finally, their application potential is summarized.

Applications of 2D MXenes in energy conversion and storage systems

The scalable and sustainable manufacture of thick electrode films with high energy and power densities is critical for the large-scale storage of electrochemical energy for application in transportation and stationary electric grids. Two-dimensional nanomaterials have become the predominant choice of electrode material in the pursuit of high energy and power densities owing to their large surface-area-to-volume ratios and lack of solid-state diffusion1,2. However, traditional electrode fabrication methods often lead to restacking of two-dimensional nanomaterials, which limits ion transport in thick films and results in systems in which the electrochemical performance is highly dependent on the thickness of the film1-4. Strategies for facilitating ion transport-such as increasing the interlayer spacing by intercalation5-8 or introducing film porosity by designing nanoarchitectures9,10-result in materials with low volumetric energy storage as well as complex and lengthy ion transport paths that impede performance at high charge-discharge rates. Vertical alignment of two-dimensional flakes enables directional ion transport that can lead to thickness-independent electrochemical performances in thick films11-13. However, so far only limited success11,12 has been reported, and the mitigation of performance losses remains a major challenge when working with films of two-dimensional nanomaterials with thicknesses that are near to or exceed the industrial standard of 100 micrometres. Here we demonstrate electrochemical energy storage that is independent of film thickness for vertically aligned two-dimensional titanium carbide (Ti3C2T x ), a material from the MXene family (two-dimensional carbides and nitrides of transition metals (M), where X stands for carbon or nitrogen). The vertical alignment was achieved by mechanical shearing of a discotic lamellar liquid-crystal phase of Ti3C2T x . The resulting electrode films show excellent performance that is nearly independent of film thickness up to 200 micrometres, which makes them highly attractive for energy storage applications. Furthermore, the self-assembly approach presented here is scalable and can be extended to other systems that involve directional transport, such as catalysis and filtration.

Thickness-independent capacitance of vertically aligned liquid-crystalline MXenes.

Li–air(O2) and Li–S batteries have gained much attention recently and most relevant research has aimed to improve the electrochemical performance of air(O2) or sulfur cathode materials. However, many technical problems associated with the Li metal anode have yet to be overcome. This review mainly focuses on the electrochemical behaviors and technical issues related to metallic Li anode materials as well as other metallic anode materials such as alkali (Na) and alkaline earth (Mg) metals, including Zn and Al when these metal anodes were employed for various types of secondary batteries.

Metallic anodes for next generation secondary batteries.

Two-dimensional transition-metal carbide materials (termed MXene) have attracted huge attention in the field of electrochemical energy storage due to their excellent electrical conductivity, high volumetric capacity, etc. Herein, with inspiration from the interesting structure of pillared interlayered clays, we attempt to fabricate pillared Ti3C2 MXene (CTAB–Sn(IV)@Ti3C2) via a facile liquid-phase cetyltrimethylammonium bromide (CTAB) prepillaring and Sn4+ pillaring method. The interlayer spacing of Ti3C2 MXene can be controlled according to the size of the intercalated prepillaring agent (cationic surfactant) and can reach 2.708 nm with 177% increase compared with the original spacing of 0.977 nm, which is currently the maximum value according to our knowledge. Because of the pillar effect, the assembled LIC exhibits a superior energy density of 239.50 Wh kg–1 based on the weight of CTAB–Sn(IV)@Ti3C2 even under higher power density of 10.8 kW kg–1. When CTAB–Sn(IV)@Ti3C2 anode couples with commercial AC ...

Pillared Structure Design of MXene with Ultralarge Interlayer Spacing for High-Performance Lithium-Ion Capacitors.

Two-dimensional transition metal carbide materials called MXenes show potential application for energy storage due to their remarkable electrical conductivity and low Li+ diffusion barrier. However, the lower capacity of MXene anodes limits their further application in lithium-ion batteries. Herein, with inspiration from the unique metal ion uptake behavior of highly conductive Ti3C2 MXene, we overcome this impediment by fabricating Sn4+ ion decorated Ti3C2 nanocomposites (PVP-Sn(IV)@Ti3C2) via a facile polyvinylpyrrolidone (PVP)-assisted liquid-phase immersion process. An amorphous Sn(IV) nanocomplex, about 6–7 nm in lateral size, has been homogeneously anchored on the surface of alk-Ti3C2 matrix by ion-exchange and electrostatic interactions. In addition, XRD and TEM results demonstrate the successful insertion of Sn4+ into the interlamination of an alkalization-intercalated Ti3C2 (alk-Ti3C2) matrix. Due to the possible “pillar effect” of Sn between layers of alk-Ti3C2 and the synergistic effect between...

Sn4+ Ion Decorated Highly Conductive Ti3C2 MXene: Promising Lithium-Ion Anodes with Enhanced Volumetric Capacity and Cyclic Performance

Electrochemical investigation of TiO2/carbon nanotubes nanocomposite as anode materials for lithium-ion batteries

One-pot Biotemplate Synthesis of FeS2 Decorated Sulfur-doped Carbon Fiber as High Capacity Anode for Lithium-ion Batteries

Lithium–sulfur batteries have attracted significant attention recently due to their high theoretical capacity, energy density and cost effectiveness. However, sulfur cathodes suffer from issues such as shuttle effects, uncontrollable deposition of lithium sulfides species, and volume expansion of sulfur, which result in rapid capacity fading and low Coulombic efficiency. In recent years, metal-oxide nanostructures have been widely used in Li–S batteries, owing to their effective inhibition of the shuttle effect and controlled deposition of lithium sulfide. However, the nonconductive metal-oxides used in Li–S batteries suffer from extra diffusion process, which slows down the electrochemical reaction kinetics. Herein, we report the synthesis of carbon nanoflakes decorated with conductive aluminium-doped zinc oxide (AZO@C) nanoparticles, through a facile biotemplating method using kapok fibers as both the template and carbon source. A sulfur cathode based on the AZO@C nanocomposites shows better electrochemical performance than those of cathodes based on ZnO and Al2O3 with poor conductivity, with a stable capacity of 927 mAh·g−1 at 0.1C (1C = 1,675 mA·g−1) after 100 cycles. A reversible capacity of 544 mAh·g−1 after 300 cycles was obtained even after increasing the current density to 0.5C, with a 0.039% capacity decay per cycle under a sulfur loading of 3.3 mg·cm−2. Moreover, a capacity of 466 mAh·g−1 after 100 cycles at 0.5C could still be obtained when the sulfur loading was increased to 6.96 mg·cm−2. The excellent electrochemical performance of the AZO@C/S composite can be attributed to its high conductivity of the polar AZO host, which suppresses the shuttle effect while simultaneously improving the redox kinetics in the reciprocal transformation of lithium sulfide species.

Liyuan Zhang

Papers

Pillared Structure Design of MXene with Ultralarge Interlayer Spacing for High-Performance Lithium-Ion Capacitors.

Sn4+ Ion Decorated Highly Conductive Ti3C2 MXene: Promising Lithium-Ion Anodes with Enhanced Volumetric Capacity and Cyclic Performance

Electrochemical investigation of TiO2/carbon nanotubes nanocomposite as anode materials for lithium-ion batteries

One-pot Biotemplate Synthesis of FeS2 Decorated Sulfur-doped Carbon Fiber as High Capacity Anode for Lithium-ion Batteries

Enhanced sulfide chemisorption by conductive Al-doped ZnO decorated carbon nanoflakes for advanced Li–S batteries