Ultrafine Titanium Nitride Sheath Decorated Carbon Nanofiber Network Enabling Stable Lithium Metal Anodes

Abstract

Nonuniform local electric field and few nucleation sites on the reactive interface tend to cause detrimental lithium (Li) dendrites, which incur severe safety hazards and hamper the practical application of Li metal anodes in batteries. Herein, a carbon nanofiber (CNF) mat decorated with ultrafine titanium nitride (TiN) nanoparticles (CNF‐TiN) as both current collector and host material is reported for Li metal anodes. Uniform Li deposition is achieved by a synergetic effect of lithiophilic TiN and 3D CNF configuration with a highly conductive network. Theoretical calculations reveal that Li prefers to be adsorbed onto the TiN sheath with a low diffusion energy barrier, leading to controllable nucleation sites and dendrite‐free Li deposits. Moreover, the pseudocapacitive behavior of TiN identified through kinetics analysis is favorable for ultrafast Li+ storage and the charge transfer process, especially under a high plating/stripping rate. The CNF‐TiN‐modified Li anodes deliver lower nucleation overpotential for Li plating and superior electrochemical performance under a large current density (200 cycles at 3 mA cm−2) and high capacity (100 cycles with 6 mAh cm−2), as well as a long‐running lifespan (>600 h). The CNF‐TiN‐based full cells using lithium iron phosphate and sulfur cathodes exhibit excellent cycling stability.

Thermal pyrolysis of Si@ZIF-67 into Si@N-doped CNTs towards highly stable lithium storage

“…, where k 1 v and k 2 v 1/2 are related to pseudocapacitive behavior and diffusion-controlled insertion, respectively [43]. The capacitive charge storage contributions to the entire CV curves of Si@N-doped CNTs at various scan rates are shown in Fig.…”

Advances in the Design of 3D‐Structured Electrode Materials for Lithium‐Metal Anodes

“…Selfsupported carbon nanofibers are the preferred carbon frame, as they exhibit the advantages of high specific open surface area, macroporous structure, and well-defined conducting network, and can be easily fabricated by electrospinning. [110][111][112][113][114] Ag, [110] TiN, [111] Li 6.4 La 3 Zr 2 Al 0.2 O 12 , [112] Sn, [113] and Cu nanoparticles [114] were used as lithiophilic materials on the surface of carbon networks, and the resulting composites delivered high areal and volumetric capacities of 16 mAh cm −2 and 1600 mAh cm −3 , respectively, which led to a low overpotential of <25 mV and a long lifetime of 1000 h (Figure 7a). [110][111][112][113][114] As a carbon framework, GNSs with a large surface area and oxygenated functional groups were also used in combination with lithiophilic metal-based Reproduced with permission.…”

A Dual‐Functional Conductive Framework Embedded with TiN‐VN Heterostructures for Highly Efficient Polysulfide and Lithium Regulation toward Stable Li–S Full Batteries

“…To assess the electrochemical reversibility and stability of Li/TiN‐VN@CNF and bare Li anode, the Coulombic efficiency (CE) measurements were performed coupled with Cu foil, as shown in Figure S23 (Supporting Information). The Li/TiN‐VN@CNFs‐Cu cell could deliver stable CE and voltage curves over 200 cycles while the Li‐Cu cell present huge fluctuations and rapid decline of the CE, indicating the higher Li consumption caused by inhomogeneous Li deposition in the depositing/striping process of the bare Li electrode …”