Mitigating Concentration Polarization through Acid-Base Interaction Effects for Long-Cycling Lithium Metal Anodes.

Lithium (Li) metal has attracted great attention as a promising high-capacity anode material for next-generation high-energy-density rechargeable batteries. Nonuniform Li+ transport and uneven Li plating/stripping behavior are two key factors that deteriorate the electrochemical performance. In this work, we propose an interphase acid-base interaction effect that could regulate Li plating/stripping behavior and stabilize the Li metal anode. ZSM-5, a class of zeolites with ordered nanochannels and abundant acid sites, was employed as a functional interface layer to facilitate Li+ transport and mitigate the cell concentration polarization. As a demonstration, a pouch cell with a high-areal-capacity LiNi0.95Co0.02Mn0.03O2 cathode (3.7 mAh cm-2) and a ZSM-5 modified thin lithium anode (50 µm) delivered impressive electrochemical performance, showing 92% capacity retention in 100 cycles (375.7 mAh). This work reveals the effect of acid-base interaction on regulating lithium plating/stripping behaviors, which could be extended to developing other high-performance alkali metal anodes.

Manipulating Redox Kinetics of Sulfur Species Using Mott-Schottky Electrocatalysts for Advanced Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries suffer from sluggish sulfur redox reactions under high-sulfur-loading and lean-electrolyte conditions. Herein, a typical Co@NC heterostructure composed of Co nanoparticles and a semiconductive N-doped carbon matrix is designed as a model Mott-Schottky catalyst to exert the electrocatalytic effect on sulfur electrochemistry. Theoretical and experimental results reveal the redistribution of charge and a built-in electric field at the Co@NC heterointerface, which are critical to lowering the energy barrier of polysulfide reduction and Li2S oxidation in the discharge and charge process, respectively. With Co@NC Mott-Schottky catalysts, the Li-S batteries display an ultrahigh capacity retention of 92.1% and a system-level gravimetric energy density of 307.8 Wh kg-1 under high S loading (10.73 mg cm-2) and lean electrolyte (E/S = 5.9 µL mgsulfur-1) conditions. The proposed Mott-Schottky heterostructure not only deepens the understanding of the electrocatalytic effect in Li-S chemistry but also inspires a rational catalyst design for advanced high-energy-density batteries.

Engineering a Low-Strain Si@TiSi2@NC Composite for High-Performance Lithium-Ion Batteries.

The huge volume expansion/contraction of silicon (Si) during the lithium (Li) insertion/extraction process, which can lead to cracking and pulverization, poses a substantial impediment to its practical implementation in lithium-ion batteries (LIBs). The development of low-strain Si-based composite materials is imperative to address the challenges associated with Si anodes. In this study, we have engineered a TiSi2 interface on the surface of Si particles via a high-temperature calcination process, followed by the introduction of an outermost carbon (C) shell, leading to the construction of a low-strain and highly stable Si@TiSi2@NC composite. The robust TiSi2 interface not only enhances electrical and ionic transport but also, more critically, significantly mitigates particle cracking by restraining the stress/strain induced by volumetric variations, thus alleviating pulverization during the lithiation/delithiation process. As a result, the as-fabricated Si@TiSi2@NC electrode exhibits a high initial reversible capacity (2172.7 mAh g-1 at 0.2 A g-1), superior rate performance (1198.4 mAh g-1 at 2.0 A g-1), and excellent long-term cycling stability (847.0 mAh g-1 after 1000 cycles at 2.0 A g-1). Upon pairing with LiNi0.6Co0.2Mn0.2O2 (NCM622), the assembled Si@TiSi2@NC||NCM622 pouch-type full cell exhibits exceptional cycling stability, retaining 90.1% of its capacity after 160 cycles at 0.5 C.

Locking Active Li Metal through Localized Redistribution of Fluoride Enabling Stable Li-Metal Batteries.

The creation of fluorinated interphase has emerged as an effective strategy for improving Li-metal anodes for rechargeable high-energy batteries. In contrast to the introduction of fluorine-containing species through widely adopted electrolyte engineering, a Li-metal composite design is reported in which LiF can locally redistribute on the Li-metal surface in liquid electrolytes via a dissolution-reprecipitation mechanism, and enable the formation of a high-fluorine-content solid electrolyte interphase (SEI). For validation, a Li/Li22 Sn5 /LiF ternary composite is investigated, where the as-formed LiF-rich SEI locks the active Li metal from corrosive electrolyte. The Li/Li22 Sn5 /LiF anode displays an impressive average Coulombic efficiency (ACE, ≈99.2%) at 1 mA cm-2 and 1 mAh cm-2 in a carbonate electrolyte and a remarkable cycling life of over 1600 h at 1 mA cm-2 and 2 mAh cm-2 . Applied to a LiCoO2 full cell with a high cathode areal capacity of 4.0 mAh cm-2 , a high capacity retention of ≈91.1% is realized for 100 cycles at 0.5 C between 2.8 to 4.5 V with a low negative/positive (N/P) ratio of 2:1. This design is conceptually different from the design employing the widely used fluorine-containing electrolyte additive and provides an alternative approach to realize reliable Li-metal batteries.

Hybrid Polymer-Alloy-Fluoride Interphase Enabling Fast Ion Transport Kinetics for Low-Temperature Lithium Metal Batteries.

Low-temperature lithium metal batteries are of vital importance for cold-climate condition applications. Their realization, however, is plagued by the extremely sluggish Li+ transport kinetics in the vicinity of Li metal anode at low temperatures. Different from the widely adopted electrolyte engineering, a functional interphase design concept is proposed in this work to efficiently improve the low-temperature electrochemical reaction kinetics of Li metal anodes. As a proof of concept, we design a hybrid polymer-alloy-fluoride (PAF) interphase featuring numerous gradient fluorinated solid-solution alloy composite nanoparticles embedded in a polymerized dioxolane matrix. Systematic experimental and theoretical investigations demonstrate that the hybrid PAF interphase not only exhibits superior lithiophilicity but also provides abundant ionic conductive pathways for homogeneous and fast Li+ transport at the Li-electrolyte interface. With enhanced interfacial dynamics of Li-ion migration, the as-designed PAF-Li anode works stably for 720 h with low voltage hysteresis and dendrite-free electrode morphology in symmetric cell configurations at -40 °C. The full cells with PAF-Li anode display a commercial-grade capacity of 4.26 mAh cm-2 and high capacity retention of 74.7% after 150 cycles at -20 °C. The rational functional interphase design for accelerating ion-transfer kinetics sheds innovative insights for developing high-areal-capacity and long-lifespan lithium metal batteries at low temperatures.