Redox-Driven Lithium Perfusion to Fabricate Li@Ni–Foam Composites for High Lithium-Loading 3D Anodes

Abstract

As the hostless nature of the conventional Li anodes with planar surfaces inevitably causes volume expansion and parasitic dendrite growth, it is essential to develop a composite electrode structure with improved Li plating/ stripping behaviors to mitigate such issues. Herein, a composite Li@NF anode was successfully fabricated through lithium perfusion into the commercial nickel foam (NF) decorated with lithiophilic NiO nanosheets, demonstrating an exceptionally high areal Li loading of 53.2 mg cm −2 with suppressed Li dendrite formation and volume expansion, improved Coulombic efficiency, as well as extended cycling stability in all half, symmetric, and full cell tests. More importantly, density functional theory calculations and control studies with Fe 2 O 3 @NF, pristine NF, and Cu 2 O@CF reveal a linear correlation between the thermodynamics of the surface reactions and the lithiophilicity of the reaction products, attesting to a redox-driven Li perfusion process. Further, through ex situ scanning electron and in situ optical microscopy, the enhanced performance of Li@NF is mainly attributed to the mediation of Li plating/stripping through homogenizing the Li + flux, decentralizing local charge density, and accommodating multidirectional Li deposition by the conductive 3D scaffolds. Consequently, this study offers important insights into the driving of thermal Li perfusion through appropriate material and surface design for achieving safe and stable lithium metal anodes.

Bottom-Up Li Deposition by Constructing a Multiporous Lithiophilic Gradient Layer on 3D Cu Foam for Stable Li Metal Anodes

“…4 Replacing two-dimensional (2D) Cu foil current collectors with three-dimensional (3D) metallic foams could enable the deposition of Li into the pores of the foams, thus suppressing the volume effect. 5 Nevertheless, uneven Li deposition within fresh 3D metallic foam can be observed during repeated Li plating/stripping; 6,7 specifically, Li preferentially nucleates on the top surface and blocks the Li diffusion channels to the bottom of the 3D foam. This restricts the full utilization of the abundant interior space, substantially impairing the functioning of 3D-framework current collectors with regard to Li plating.…”

“…Replacing two-dimensional (2D) Cu foil current collectors with three-dimensional (3D) metallic foams could enable the deposition of Li into the pores of the foams, thus suppressing the volume effect . Nevertheless, uneven Li deposition within fresh 3D metallic foam can be observed during repeated Li plating/stripping; , specifically, Li preferentially nucleates on the top surface and blocks the Li diffusion channels to the bottom of the 3D foam. This restricts the full utilization of the abundant interior space, substantially impairing the functioning of 3D-framework current collectors with regard to Li plating. , To date, numerous ingenious strategies have been developed to modify 3D foam current collectors, and these strategies mainly include (i) constructing a 3D porous metallic current collector that effectively reduces the exchange current densities in the microregions of the electrode, ensures good contact, and increases tolerance to spatial volume expansion upon localized uncontrollable and substantial Li plating; − (ii) fabricating a lithiophilic alloy layer with a 3D porous metallic current collector (e.g., Cu or Ni foam) from an architecture-design perspective − decreases the Li nucleation barrier and homogenizes the mass transfer of the Li-ion flux; and (iii) fabricating artificial solid electrolyte interface (SEI) films on 3D porous current collectors to suppress direct contact between metallic lithium and the electrolyte, − thus prohibiting successive electrolyte decomposition.…”

Rational design of a self-supporting skeleton decorated with dual lithiophilic Sn-containing and N-doped carbon tubes for dendrite-free lithium metal anodes

“…19 However, commercial metal-based skeletons, such as Ni foam (NF) and Cu foam (CF), could hardly suppress effectively the formation of dendritic Li, so various measures have been taken to increase their lithiophilicity or flexibility. The introduction of lithiophilic metal or metal oxide nanoparticles such as Au, 20 Ag, 21 SnO 2 , 22 V 2 O 5 , 23 ZnO, 24,25 Zn, 26 CoO, 27 and NiO 28 into metal foams could regulate positively the Li plating/stripping behaviors, so that the dendrites and dead Li could be eliminated to some extent. Common CF coated with a polymer protective layer is beneficial for achieving superior electrochemical performance through suppressing the formation of dendritic Li by the high Young's modulus.…”

Interphase Building of Organic–Inorganic Hybrid Polymer Solid Electrolyte with Uniform Intermolecular Li+ Path for Stable Lithium Metal Batteries

“…[8] Nevertheless, two crucial scientific issues associated with Li metal electrode are unstable solid electrolyte interphase (SEI) and the Li dendrite growth on lithium plating/stripping, [9] which lead to fast consumption of electrolyte and Li metal, further resulting in electrolyte "dryout," early failure of the battery and low coulombic efficiency (CE). [10,11] Till now, tremendous efforts have been devoted to tackling the intrinsic defects by novel design of electrode structure, [12][13][14][15][16][17] electrolyte modification, [18,19] embellishment of lithium with artificial solid electrolyte interphase (artificial SEI) layers, [20][21][22][23] and etc. [24,48] Lithium (Li) metal has been generally noticed as the most prospective anode for next-generation batteries attributed to its outstanding theoretical capacity and low electrochemical potential.…”