Synergistic Manipulation of Zn²⁺ Ion Flux and Nucleation Induction Effect Enabled by 3D Hollow SiO₂/TiO₂/Carbon Fiber for Long‐Lifespan and Dendrite‐Free Zn–Metal Composite Anodes

Abstract

Aqueous rechargeable zinc-metal batteries are a promising candidate for next-generation energy storage devices due to their intrinsic high capacity, low cost, and high safety. However, uncontrollable dendrite formation is a serious problem, resulting in limited lifespan and poor coulombic efficiency of zinc-metal anodes. To address these issues, a 3D porous hollow fiber scaffold with well-dispersed TiO 2 , SiO 2 , and carbon is used as superzincophilic host materials for zinc anodes. The amorphous TiO 2 and SiO 2 allow for controllable nucleation and deposition of metal Zn inside the porous hollow fiber even at ultrahigh current densities. Furthermore, the as-fabricated interconnected conductive hollow SiO 2 and TiO 2 fiber (HSTF) possess high porosity, high conductivity, and fast ion transport. Meanwhile, the HSTF exhibits remarkable mechanical strength to sustain massive Zn loading during repeated cycles of plating/stripping. The HSTF with interconnected conductive network can build a uniform electric field, redistributing the Zn 2+ ion flux and resulting in smooth and stable Zn deposition. As a result, in symmetrical cells, the Zn@HSTF electrode delivers a long cycle life of over 2000 cycles at 20 mA cm −2 with low overpotential (≈160 mV). The excellent cycling lifespan and low polarization are also realized in Zn@HSTF//MnO 2 full cells.

Nitrogen‐Doped Carbon Fibers Embedded with Zincophilic Cu Nanoboxes for Stable Zn‐Metal Anodes

“…The cycling performance of Cu NBs@NCFs-Zn is also comparable to most of recently reported composite Zn on different hosts (Table S1, Supporting Information). [22,24,26,28,30,31,34,36,[46][47][48] Furthermore, the voltage hysteresis of the Cu NBs@NCFs-Zn electrode shows a gradual increment with the current density increasing from 0.5 to 5 mA cm −2 (Figure S29, Supporting Information), indicating the low polarization and good stability.…”

“…However, it is hard to regulate the interfacial Zn 2+ ions' distribution and enable uniform Zn deposition by only 3D hosts due to the high energy barriers of Zn nucleation. [30,31] To further prolong the lifespan of ZMAs, zincophilic species (N-doping, [31,32] Cu, [33] Zn, [34,35] TiO 2 , [21,36] Sn, [19] Ag, [37] etc.) with high adsorbing ability for Zn 2+ ions are usually introduced into the 3D conductive hosts to reinforce the interfacial interaction between substrate and Zn 2+ ions.…”

An Ultrahigh Rate and Stable Zinc Anode by Facet‐Matching‐Induced Dendrite Regulation

“…[2] Therefore, various strategies have been developed, mainly aiming at inhibiting dendrite formation, including: i) reducing Zn nucleation overpotential by improving materials' zincophilicity; [11] ii) constructing artificial anode-electrolyte interface to guide orderly Zn 2+ diffusion; [6a,12] iii) inducing planar Zn deposition by lattice matching, electrolyte adjustment, and separator modification; [6c,13] and iv) employing 3D conductive scaffolds to reduce the true current density. [14] These technologies can homogenize Zn deposition to a certain extent, however, commonly at the cost of rate capabilities. This is because the surface inhomogeneity of Zn is hard to be completely eliminated by these strategies, and the irregular Zn plating/stripping still occurs at high current densities.…”

Cable‐like V2O5 Decorated Carbon Cloth as a High‐Capacity Cathode for Flexible Zinc Ion Batteries

“…Hence, it is envisaged that this flexible cell will have enormous prospects in the market of wearable products. [ 42–46 ] For CC@V 2 O 5 , its cyclic capabilities in coin cell and pouch cell are also evidently superior to those of the previously reported V 2 O 5 ‐based and the other cathode materials (Table S1 and S2, Supporting Information). Such results also demonstrate that CC@V 2 O 5 electrodes can still exhibit satisfactory capacity and prolonged lifespan at higher current densities, which is necessary for achieving high‐performance ZIBs.…”