Functionality of Dual‐Phase Lithium Storage in a Porous Carbon Host for Lithium‐Metal Anode

Abstract

Lithium (Li) metal is regarded as the most attractive anode material for high-energy Li batteries, but it faces unavoidable challenges-uncontrollable dendritic growth of Li and severe volume changes during Li plating and stripping. Herein, a porous carbon framework (PCF) derived from a metal-organic framework (MOF) is proposed as a dual-phase Li storage material that enables efficient and reversible Li storage via lithiation and metallization processes. Li is electrochemically stored in the PCF upon charging to 0 V versus Li/Li + (lithiation), making the PCF surface more lithiophilic, and then the formation of metallic Li phase can be induced spontaneously in the internal nanopores during further charging below 0 V versus Li/Li + (metallization). Based on thermodynamic calculations and experimental studies, it is shown that atomically dispersed zinc plays an important role in facilitating Li plating and that the reversibility of Li storage is significantly improved by controlled nanostructural engineering of 3D porous nanoarchitectures to promote the uniform formation of Li. Moreover, the MOF-derived PCF does not suffer from macroscopic volume changes during cycling. This work demonstrates that the nanostructural engineering of porous carbon structures combined with lithiophilic element coordination would be an effective approach for realizing high-capacity, reversible Li-metal anodes.

Recent Progress of Porous Materials in Lithium‐Metal Batteries

“…A stable and conformal SEI is formed to isolate the Li metal and electrolyte solvents, avoiding deleterious side reactions. [ 132–140 ]…”

“…A stable and conformal SEI is formed to isolate the Li metal and electrolyte solvents, avoiding deleterious side reactions. [132][133][134][135][136][137][138][139][140] In 2014, Zheng et al designed a flexible, crosslinking, porous, hollow carbon sphere to induce homogenous Li deposition. [141] The hollow carbon nanospheres were coated on the Cu substrate by the chemical process.…”

Stabilizing Li-metal host anode with LiF-rich solid electrolyte interphase

“…Based on above aspects, we have reported that the physical properties of nanoporous zeolitic imidazolate framework (ZIF)-derived carbons can be controlled by different ratios of zinc (Zn) to cobalt (Co)-ion metallic precursors [19][20][21]. This approach was designed to achieve tailored ZIF-derived carbons with different pore volumes, pore sizes, surface areas, and even degrees of graphitization.…”

Tailoring the oxygen content in lithiated silicon oxide for lithium‐ion batteries

“…1,2 Graphite is the most broadly used and commercialized anode material for LIBs; however, owing to its limited theoretical capacity (372 mAh/g), it cannot fully meet the demand for high capacity. [3][4][5] Silicon has recently emerged as a promising alternative to graphite as an anode for LIBs due to its exceptionally high theoretical capacity (Li 15 Si 4 , 3580 mA h g −1 ). 6,7 However, the practical utilization of silicon anode is hindered by a severe volume change of up to 300% during cycling.…”

“…Substantial effort has been exerted to identify a new anode material with a high capacity, long cycle performance, high power density, and high coulombic efficiency for lithium‐ion batteries (LIBs) 1,2 . Graphite is the most broadly used and commercialized anode material for LIBs; however, owing to its limited theoretical capacity (372 mAh/g), it cannot fully meet the demand for high capacity 3‐5 …”