Two Birds with One Stone: Using Indium Oxide Surficial Modification to Tune Inner Helmholtz Plane and Regulate Nucleation for Dendrite‐free Lithium Anode

Abstract

Lithium metal has been considered as the most promising anode material due to its distinguished specific capacity of 3860 mAh g–1 and the lowest reduction potential of ‐3.04 V versus the Standard Hydrogen Electrode. However, the practicalization of Li‐metal batteries (LMBs) is still challenged by the dendritic growth of Li during cycling, which is governed by the surface properties of the electrodepositing substrate. Herein, a surface modification with indium oxide on the copper current collector via magnetron sputtering, which can be spontaneously lithiated to form a composite of lithium indium oxide and Li‐In alloy, is proposed. Thus, the growth of Li dendrites is effectively suppressed via regulating the inner Helmholtz plane modified with LiInO2 to foster the desolvation of Li‐ion and induce the nucleation of Li‐metal in two‐dimensions through electro‐crystallization with Li‐In alloy. Using the In2O3 modification, the Li‐metal anode exhibits outstanding cyclic stability, and LMBs with lithium cobalt oxide cathode present excellent capacity retention (above 80% over 600 cycles). Enlightening, the scalable magnetron sputtering method reported here paves a novel way to accelerate the practical application of the Li anode in LMBs to pursue higher energy density.

Lithiophilic Interphase Porous Buffer Layer toward Uniform Nucleation in Lithium Metal Anodes

“…Veritably, a Helmholtz plane exists between the Cu's surface and electrolytes owing to dielectric difference. [ 27 ] The inner Helmholtz plane mainly affects the desolvation of lithium ions. [ 28 ] While the stability of solid–liquid interface and lithium ion transport kinetics are governed by the lithium ion solvation.…”

“…[ 28 ] In addition, the nucleation and further growth morphology of desolvated Li are related to the substrate. [ 27 ] Reasonably, surface modification for the Cu substrate with effectual and lithiophilic protective layer can be expected to prolong lifetime of LMBs. It presents side reactions of organic electrolyte on the Cu surface during electrochemical process of deposition and stripping and governs uniform electrodeposition of Li.…”

“…The high surface energy can bolster the self‐diffusion of Li atom on the substrate and shift the nucleation type to higher dimensions. [ 27 ] Nonetheless, they are known for the poor electro‐conductivity, which leads to considerable internal resistance, large polarization, and insufficient Li deposition kinetics during long‐term cycles. [ 29 ] Exhilaratingly, lithiophilic transition metal nitrides with metallic properties can be used to supplement for the deficiency.…”

High Utilization of Composite Magnesium Metal Anodes Enabled by a Magnesiophilic Coating

“…From the electrochemical impedance spectroscopy (EIS) plots (Figure S9), charge transfer resistance ( R ct ) is seen to experience sharp reduction by replacing bare Cu (119.0 kΩ) with Au–Cu electrodes (87.7 kΩ). The low deposition overpotentials and small interfacial impedance show that the highly magnesiophilic Au coating facilitates fast Mg transport at the electrolyte/electrode interface and subsequent deposition on the electrode surface. − …”

Eliminating Lightning‐Rod Effect of Lithium Anodes via Sine‐Wave Analogous MXene Layers

“…[9][10][11][12] A large number of theoretical and experimental studies demonstrate that Li dendrite generation mainly originates from the inhomogeneous nucleation of metallic Li as well as the huge concentration gradient of lithium ion and nonuniform electric field. [13][14][15][16] Thus, Many strategies have been proposed to solve the intricate Li dendrite problems. On the one hand, strategies by utilizing lithiophilicity (lithiophilic sites, metal solid solutions, or chemical bonding) at the initial deposition stage can…”