Ultra-Efficient Synthesis of Nb4 C3 Tx MXene via H2 O-Assisted Supercritical Etching for Li-Ion Battery.

Nb4 C3 Tx MXene has shown extraordinary promise for various applications owing to its unique physicochemical properties. However, it can only be synthesized by the traditional HF-based etching method, which uses large amounts of hazardous HF and requires a long etching time (> 96 h), thus limiting its practical application. Here, an ultra-efficient and environmental-friendly H2 O-assisted supercritical etching method is proposed for the preparation of Nb4 C3 Tx MXene. Benefiting from the synergetic effect between supercritical CO2 (SPC-CO2 ) and subcritical H2 O （SBC-H2 O）, the etching time for Nb4 C3 Tx MXene can be dramatically shortened to 1 h. The as-synthesized Nb4 C3 Tx MXene possesses uniform accordion-like morphology and large interlayer spacing. When used as anode for Li-ion battery, the Nb4 C3 Tx MXene delivers a high reversible specific capacity of 430 mAh g-1 at 0.1 A g-1 , which is among the highest values achieved in pure-MXene-based anodes. The superior lithium storage performance of the Nb4 C3 Tx MXene can be ascribed to its high conductivity, fast Li+ diffusion kinetics and good structural stability.

NH3-Induced In Situ Etching Strategy Derived 3D-Interconnected Porous MXene/Carbon Dots Films for High Performance Flexible Supercapacitors.

2D MXene (Ti3CNTx) has been considered as the most promising electrode material for flexible supercapacitors owing to its metallic conductivity, ultra-high capacitance, and excellent flexibility. However, it suffers from a severe restacking problem during the electrode fabrication process, limiting the ion transport kinetics and the accessibility of ions in the electrodes, especially in the direction normal to the electrode surface. Herein, we report a NH3-induced in situ etching strategy to fabricate 3D-interconnected porous MXene/carbon dots (p-MC) films for high-performance flexible supercapacitor. The pre-intercalated carbon dots (CDs) first prevent the restacking of MXene to expose more inner electrochemical active sites. The partially decomposed CDs generate NH3 for in situ etching of MXene nanosheets toward 3D-interconnected p-MC films. Benefiting from the structural merits and the 3D-interconnected ionic transmission channels, p-MC film electrodes achieve excellent gravimetric capacitance (688.9 F g-1 at 2 A g-1) and superior rate capability. Moreover, the optimized p-MC electrode is assembled into an asymmetric solid-state flexible supercapacitor with high energy density and superior cycling stability, demonstrating the great promise of p-MC electrode for practical applications.

Vertical-MXene based micro-supercapacitors with thickness-independent capacitance.

MXenes have shown great potential as an emerging two-dimensional (2D) material for micro-supercapacitors (MSCs) due to their high conductivity, rich surface chemistry, and high capacity. However, MXene sheets inherently tend to lay flat on the substrate during film formation to assemble into compact stacked structures, which hinders ion accessibility and prolongs ion transport paths, leading to highly dependent electrochemical properties on the thickness of the film. Here, we demonstrate a vertically aligned Ti3C2Tx MXene based micro-supercapacitor with an excellent electrochemical performance by a liquid nitrogen-assisted freeze-drying method. The vertical arrangement of the 2D MXene sheets allows for directional ion transport, enabling the vertical-MXene based MSCs to exhibit thickness-independent electrochemical properties even in thick films. In addition, the MSCs displayed a high areal capacitance of 87 mF cm-2 at 10 mV s-1 along with an excellent stability of ∼87.4% after 10 000 charge-discharge cycles. Furthermore, the vertical-MXene approach proposed here is scalable and can be extended to other systems involving directional transport.

Ti3C2Tx MXene-Based Micro-Supercapacitors with Ultrahigh Volumetric Energy Density for All-in-One Si-Electronics.

MXene-based microsupercapacitors (MSCs) have promoted the development of on-chip energy storage for miniaturized and portable electronics due to the small size, high power density and integration density. However, restricted energy density and operating voltage invariably create obstacles to the practical application of MSCs. Here, we report a symmetric MXene-based on-chip MSC, achieving an ultrahigh energy density of 75 mWh cm-3 with high operating voltage of 1.2 V, which are almost the highest values among all reported symmetric MXene MSCs. The adjustment strategy of acetone on the viscosity and surface tension of MXene ink, along with the natural sedimentation strategy, can effectively prevent the orderly stacking of MXene sheets. Further, we developed an all-in-one Si-electronics with three series MSCs through laser-etching technology, obviously presenting high integration capacity and processing compatibility. Thus, this work will contribute to the development of high integration all-in-one electronics with high energy density MXene-based MSCs.

Air-Stable Conductive Polymer Ink for Printed Wearable Micro-Supercapacitors.

Printed electronics are expected to facilitate the widespread distributed wearable electronics in the era of the Internet of things. However, developing cheap and stable electrode inks remains a significant challenge in the printed electronics industry and academic community. Here, overcoming the weak hydrophilicity of polyaniline, a low-cost, easy-fabricating, and air-stable conducting polymer (CP) ink is devised through a facile assemble-disperse strategy delivering a high conductivity in the order of 10-2 S cm-1 along with a remarkable specific capacitance of 386.9 F g-1 at 0.5 A g-1 (dehydrated state). The additive-free CP ink is directly employed to print wearable micro-supercapacitors (MSCs) via the spray-coating method, which deliver a high areal capacitance (96.6 mF cm-2 ) and volumetric capacitance (26.0 F cm-3 ), outperforming most state-of-the-art CP-based supercapacitors. This work paves a new approach for achieving scalable MSCs, thus rendering a cost-effective, environmentally friendly, and pervasive energy solution for next-generation distributed electronics.

Solving Gravimetric-Volumetric Capacitive Paradox of 2D Materials through Dual-Functional Chemical Bonding-Induced Self-Constructing Graphene-MXene Monoliths.

High electrical conductivity and all-open microstructure characteristics intrinsically endow both graphene and MXenes with superior electrochemical energy storage capability. However, the above two-dimensional (2D) thicker electrodes (>20 µm) severely dilute their unique rapid electronic-ionic transferring characteristic, posing a paradox of high gravimetric and high volumetric capacitive properties due to massively excessive macropores or an unduly restacked issue. Herein, we elaborately construct novel monolithic NH2-graphene and Ti3C2Tx MXene (NG@MX) composites through dual-functional induced self-assembly with the help of both covalent and hydrogen bonding interactions. Notably, much thicker monolithic NG@MX electrodes (>90 µm) fabricated by a conventional roll-coating method without any further compaction treatment can simultaneously deliver two times gravimetric (gra.) and volumetric (vol.) performance than those of pure graphene (in vol.) or MXene (in gra.) materials. Moreover, monolithic NG@MX-based supercapacitors can remarkably present two times energy density as that of graphene and four times as MXene, respectively. Such greatly enhanced electrochemical properties are closely related to the appropriate equilibrium of the volumetric density and the open structure, which can effectively guarantee the rapid transfer of both electrons and ions in the thick monolithic NG@MX electrodes. Undoubtedly, dual-functional chemical bonding-induced self-constructing NG@MX monoliths efficiently solve the long-existing gra. and vol. capacitive paradox of the thicker 2D materials used in supercapacitors, which will guide the design of high-performance capacitive materials and promote their practical application in electrochemical energy storage.

Strong Lewis Acid-Base and Weak Hydrogen Bond Synergistically Enhancing Ionic Conductivity of Poly(ethylene oxide)@SiO2 Electrolytes for a High Rate Capability Li-Metal Battery.

Solid-state composite polymer electrolytes (CPEs) usually suffer from intrinsic low ionic conductivity and a solid-solid interface, badly inhibiting their widespread commercial application in all-solid-state Li-metal battery (ASSLMB) energy storage. Herein, a synergetic strategy using strong Lewis acid-base and weak hydrogen bonds was employed for self-assembly in situ construction of three-dimensional (3D) network-structured poly(ethylene oxide) (PEO) and SiO2 CPEs (PEO@SiO2). Ascribed to this synergistically rigid-flexible coupling dynamic strategy, a harmonious incorporation of monodispersed SiO2 nanoparticles into PEO could remarkably reduce crystallinity of PEO, significantly enhancing the ionic conductivity (∼1.1 × 10-4 S cm-1 at 30 °C) and dramatically facilitating solid electrolyte interface stabilization (electrochemical stability window > 4.8 V at 90 °C). Moreover, the PEO@SiO2-based ASSLMBs possess excellent rate capability over a wide temperature range (∼105 mA h g-1 under 2 C at 90 °C), high temperature cycling capacity (retaining 90 mA h g-1 after 100 cycles at 90 °C), and high specific capacity (146 mA h g-1 under 0.3 C at 90 °C). Unambiguously, these high ionic conductivity CPEs along with excellent flexibility and safety can be one of the most promising candidates for high-performance ASSLMBs, evidently revealing that this synergistically rigid-flexible coupling dynamic strategy will open up a way to exploit the novel high ionic conductivity solid-state electrolytes.