A Carbon/Titanium Vanadium Nitride Composite for Lithium Storage

Abstract

In recent years, substantial efforts have been made with regard to the explorations of novel anode materials for lithium batteries with superior recharging-ability and minimal capacity fade. Among a variety of options, carbonaceous materials are promising candidates.[1] Graphite is widely used nowadays as anodes in commercial cells, [2] nevertheless its capacity is restricted to 372 mAh g À1 (maximum stage by forming LiC 6 ).Therefore, extensive research is currently focusing on the electrochemical performance of carbon-based composites which promise advantages for lithium-storage applications owing to their intrinsic characteristics possessing a vast number of active sites and offering presuppositions for a fast electronic and ionic transporting network. [3] On the other hand, low cost, high molar density and superior chemical resistance of the transition metal nitrides render them desirable candidates for the next-generation of lithium batteries and supercapacitors. [4] Among them, TiN was reported to possess a good electronic conductivity but with minor capacity and hence usually used as current collector, whereas VN was reported to exhibit a larger capacity for thin film lithium battery and supercapacitor applications despite poor electronic conductivity.[5] Therefore a composite of titanium-vanadium nitride and carbon (TiVN/C) can be expected to deliver the ingredients for efficient transport and storage. The concept of establishing an effectively mixed conducting network formed by three phase composites (storage material + electronically conducting phase + ionic conductor phase) even on a nanoscale is best demonstrated by the hierarchical structure in ref.[6], which matches both high power and high energy requirements. It was furthermore reported that incorporation of vanadium in titanium nitride would stabilize the latter one as to a range of applications such as electrodes for supercapacitors. [7] To the best of our knowledge, nearly no literature exists concerning the exploitation of titanium vanadium nitrides as anode materials for lithium batteries. Since nanostructured materials have been reported to facilitate diffusion of electrolyte and improve mass transport properties of lithium ions, [8] nanostructuring together with structural and compositional control of metal nitrides becomes crucial to influencing the overall electrochemical performance. Herein, we demonstrate nanostructured composites consisting of titanium vanadium nitride and carbon to be novel anode materials with excellent performances.A facile strategy for preparation of nanostructured metal nitrides/carbon composite has been developed by Markus Antonietti's group. [9] In this work, composites of titanium vanadium nitride and carbon were synthesized by a high-temperature route using mesoporous carbon nitrides as a reactive template.[10] In order to optimize the performance of the anode, a few nanostructured composites were synthesized with the possibility to tune continuously the ratio of the metallic components. Four ethanolic prec...

NiCo2O4@TiN Core-shell Electrodes through Conformal Atomic Layer Deposition for All-solid-state Supercapacitors

“…In order to improve the rate capability of NiCo2O4 electrodes, we introduced titanium nitride (TiN) to form NiCo2O4@TiN core-shell nanostructures with NiCo2O4. TiN attracted our attention due to the following reasons: 1) TiN is already commonly used in industry for electronics and wear resistance applications due to its low cost, scalability, and superior corrosion resistance [46,47]; 2) as a metallic material, TiN offers superb electrical conductivity (4000-55500 S cm -1 ) and mechanical stability [48][49][50]; 3) previous reports have demonstrated that transition metal nitrides are capable of delivering high energy and power density as supercapacitor electrodes [51,52]. Meanwhile, by employing atomic layer deposition (ALD), we were able to conformally grow a TiN shell onto complex nanostructures such as the NiCo2O4 nanofiber arrays without altering the desired structural features of the underlying NiCo2O4 matrix.…”

Hybrid 2D–0D Graphene–VN Quantum Dots for Superior Lithium and Sodium Storage

“…[6a] Moreover, it is confirmed that VN delivers a large reversible capacity of approximate 1200 mAh g −1 , much higher than abundant of various metal nitrides previously reported because of the high valence (+3) of V in VN. Thus, VN nanoparticles, porous VN, and VN‐based composites have been widely synthesized for lithium storage by magnetron sputtering,[6a] template‐assistant, and chemical vapor deposition methods . Unfortunately, VN materials commonly accompany large volume change (≈240%, calculated based on the density of VN, Li 3 N, and V) during cycle processes, leading to severe particle–particle electronic contact loss and poor cycle performances for lithium storage.…”

“…Obviously, such high‐rate performances of G‐VNQD‐500 are superior to those reported for the most previously VN‐based materials including VN films, porous VN, Ti–VN and VN–carbon composites. [6b,c],[9a] To explore the reason of the excellent electrochemical behaviors of G‐VNQD‐500, electrochemical impedance spectroscopy (EIS) measurements were carried out after rate cycles (Figure f, Figure S6 and Table S2, Supporting Information). Interestingly, the solid electrolyte interface (SEI) and charge transfer resistances of G‐VNQD‐500 electrode are only 23.9 and 60.8 Ω, which is much lower than those of pure VN electrode (30.9 and 135.3 Ω).…”

纳米结构的过渡金属氮化物复合物储能材料

“…(TiN)具有良好的导电性和高温化学稳定性 [23] , 而文 献报道的氮化钒(VN)显示出巨大的储锂容量. 基于 [24] (如图 3 所示), 将两种氮化物的优势协同 [25] . 我们课题组在氮掺杂对石墨烯结构与储锂物…”