Tuning 4f‐Center Electron Structure by Schottky Defects for Catalyzing Li Diffusion to Achieve Long‐Term Dendrite‐Free Lithium Metal Battery

Abstract

Lithium metal is considered as the most prospective electrode for next‐generation energy storage systems due to high capacity and the lowest potential. However, uncontrollable spatial growth of lithium dendrites and the crack of solid electrolyte interphase still hinder its application. Herein, Schottky defects are motivated to tune the 4f‐center electronic structures of catalysts to provide active sites to accelerate Li transport kinetics. As experimentally and theoretically confirmed, the electronic density is redistributed and affected by the Schottky defects, offering numerous active catalytic centers with stronger ion diffusion capability to guide the horizontal lithium deposition against dendrite growth. Consequently, the Li electrode with artificial electronic‐modulation layer remarkably decreases the barriers of desolvation, nucleation, and diffusion, extends the dendrite‐free plating lifespan up to 1200 h, and improves reversible Coulombic efficiency. With a simultaneous catalytic effect on the conversions of sulfur species at the cathodic side, the integrated Li–S full battery exhibits superior rate performance of 653 mA h g −1 at 5 C, high long‐life capacity retention of 81.4% at 3 C, and a high energy density of 2264 W h kg −1 based on sulfur in a pouch cell, showing the promising potential toward high‐safety and long‐cycling lithium metal batteries.

Lithium Atom Surface Diffusion and Delocalized Deposition Propelled by Atomic Metal Catalyst toward Ultrahigh-Capacity Dendrite-Free Lithium Anode

“…The massive demands in smart portable devices, electromobility and stationary storage systems push the developments of high-energy-density battery systems. − Lithium metal anode exhibits high theoretical capacity and the low potential (−3.04 V vs SHE). , However, the dendrite resulted from random lithium plating behaviors and sluggish surface atom diffusion, and uneven solid electrolyte interphase (SEI) prevent its wide applications. − Moreover, large volumetric changes during cycling will break down the fragile SEI so that fresh SEI will be continuously formed at the Li/electrolyte interface, exhausting the limited electrolyte . These cross-linked issues would lead to severe safety problems and significantly degraded performances .…”

“…Ball-shaped Li electrodeposits dominate at a low current density, while whisker-shaped deposition appears when the localized ability of fresh formed atom exceeds the diffusion ability (Figure A). Continuously cycling, fractal dendrite will grow on the basis of the Li-whiskers and local radial stress is accumulated because of the uneven and uncontrollable deposition. , One way to suppress the formation of Li-whiskers is to reduce the local deposition current density by using three-dimensional (3D) current collectors. However, this strategy is limited by pore volumes of the 3D current collectors and fails to work when filled or blocked by the plated lithium atoms, and dendrite growth is inevitable under high plating capacity or current density.…”

Toward Dendrite-Free Metallic Lithium Anodes: From Structural Design to Optimal Electrochemical Diffusion Kinetics

“…(E) The comparison curve of the Li nucleation barriers on different electrodes in asymmetric cell. Reprinted with permission under a Creative Commons Attribution License 4.0, ref . Copyright 2022, The Authors.…”

“…With the development of artificial intelligence, machine learning offers an approach to screen more suitable catalysts or structure designs without the need of tedious experiments. ,,, For instance, besides the binding adsorption energy between lithium ion/atom and interface/host, machine learning can offer more distinction criteria for the suitability of the materials for application in Li anodes. Also, the use of machine learning is expected to accurately guide material synthesis and significantly simplify the experimental steps.…”

“…The ever-increasing dependency and demands on consumable electronics, electric vehicles (EVs), and smart grid storages have stimulated the rising demands for high-energy-density rechargeable batteries. − Although lithium-ion batteries dominate the current consumer markets, the capacities of cathodes and graphitic anodes have both reached bottlenecks. − Fortunately, the lithium metal anode has been regarded as the “Holy Grail” for high-energy-density batteries due to its unrivaled theoretical specific capacity (∼3860 mA h g –1 ), nearly 10 times higher than that of a graphite anode (∼372 mA h g –1 ), and lower electrochemical potential (∼−3.04 V) relative to the standard hydrogen electrode (SHE). − More importantly, the utilization of a Li metal anode broadens the range of applicable cathode materials, from lithium-rich intercalated cathodes (e.g., LiFePO 4 , LiCoO 2 , and LiNi x Co y Mn 1– x – y O 2 ) to lithium-free conversion cathodes (e.g., sulfur and air), for the realization of differing types of lithium batteries with higher energy densities (Figure A). − Due to these advantageous electrochemical properties, lithium metal batteries (LMBs) have the potential to reach the energy density milestone of 500 Wh kg –1 in the next few years to satisfy industrial goals and practical utilizations in EVs and grid energy storage. − …”