Toward a quantitative interfacial description of solvation for Li metal battery operation under extreme conditions.

The future application of Li metal batteries (LMBs) at scale demands electrolytes that endow improved performance under fast-charging and low-temperature operating conditions. Recent works indicate that desolvation kinetics of Li+ plays a crucial role in enabling such behavior. However, the modulation of this process has typically been achieved through inducing qualitative degrees of ion pairing into the system. In this work, we find that a more quantitative control of the ion pairing is crucial to minimizing the desolvation penalty at the electrified interface and thus the reversibility of the Li metal anode under kinetic strain. This effect is demonstrated in localized electrolytes based on strongly and weakly bound ether solvents that allow for the deconvolution of solvation chemistry and structure. Unexpectedly, we find that maximum degrees of ion pairing are suboptimal for ultralow temperature and high-rate operation and that reversibility is substantially improved via slight local dilution away from the saturation point. Further, we find that at the optimum degree of ion pairing for each system, weakly bound solvents still produce superior behavior. The impact of these structure and chemistry effects on charge transfer are then explicitly resolved via experimental and computational analyses. Lastly, we demonstrate that the locally optimized diethyl ether-based localized-high-concentration electrolytes supports kinetic strained operating conditions, including cycling down to -60 °C and 20-min fast charging in LMB full cells. This work demonstrates that explicit, quantitative optimization of the Li+ solvation state is necessary for developing LMB electrolytes capable of low-temperature and high-rate operation.

Gradient Architecture Design in Scalable Porous Battery Electrodes.

Because it has been demonstrated to be effective toward faster ion diffusion inside the pore space, low-tortuosity porous architecture has become the focus in thick electrode designs, and other possibilities are rarely investigated. To advance current understanding in the structure-affected electrochemistry and to broaden horizons for thick electrode designs, we present a gradient electrode design, where porous channels are vertically aligned with smaller openings on one end and larger openings on the other. With its 3D morphology carefully visualized by Raman mapping, the electrochemical properties between opposite orientations of the gradient electrodes are compared, and faster energy storage kinetics is found in larger openings and more concentrated active material near the separator. As further verified by simulation, this study on gradient electrode design deepens the knowledge of structure-related electrochemistry and brings perspectives in high-energy battery electrode designs.

Tunable Porous Electrode Architectures for Enhanced Li-Ion Storage Kinetics in Thick Electrodes.

Thick electrodes, although promising toward high-energy battery systems, suffer from restricted lithium-ion transport kinetics due to prolonged diffusion lengths and tortuous transport pathways. Despite the emerging low-tortuosity designs, capacity retention under higher current densities is still limited. Herein, we employ a modified ice-templating method to fabricate low-tortuosity porous electrodes with tunable wall thickness and channel width and systematically investigate the critical impacts of the fine structural parameters on the thick electrode electrochemistry. While the porous electrodes with thick walls show diminished capability under a C-rate larger than 1.5 C, those with thinner walls could maintain ∼70% capacity under 2.5 C. The superior capacity retention is ascribed to the fast diffusion into the thin lamellar walls compared with their thicker counterparts. This study provides deeper insights into structure-affected electrochemistry and opens up new perspective of 3D porous architectural designs for high-energy and high-power electrodes.

From Fundamental Understanding to Engineering Design of High-Performance Thick Electrodes for Scalable Energy-Storage Systems.

The ever-growing needs for renewable energy demand the pursuit of batteries with higher energy/power output. A thick electrode design is considered as a promising solution for high-energy batteries due to the minimized inactive material ratio at the device level. Most of the current research focuses on pushing the electrode thickness to a maximum limit; however, very few of them thoroughly analyze the effect of electrode thickness on cell-level energy densities as well as the balance between energy and power density. Here, a realistic assessment of the combined effect of electrode thickness with other key design parameters is provided, such as active material fraction and electrode porosity, which affect the cell-level energy/power densities of lithium-LiNi0.6 Mn0.2 Co0.2 O2 (Li-NMC622) and lithium-sulfur (Li-S) cells as two model battery systems, is provided. Based on the state-of-the-art lithium batteries, key research targets are quantified to achieve 500 Wh kg-1 /800 Wh L-1 cell-level energy densities and strategies are elaborated to simultaneously enhance energy/power output. Furthermore, the remaining challenges are highlighted toward realizing scalable high-energy/power energy-storage systems.

Nonflammable, Low-Cost, and Fluorine-Free Solvent for Liquid Electrolyte of Rechargeable Lithium Metal Batteries.

Rechargeable metallic lithium batteries are considered as promising candidates for next-generation energy storage due to their high energy densities. However, safety concerns associated with electrolyte flammability and dendrite growth hinder their practical applications. Nonflammable liquid electrolytes have attracted significant attention recently, but they are mainly based on expensive ionic liquids, fluorinated solvents, or with highly concentrated salt. Here we design a novel trisalt electrolyte composed of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-lithium bis(oxalato)borate (LiBOB)-LiPF6 in EC/PC solvent, which is not flammable even in contact with fire. Moreover, it creates unique protection of solid electrolyte interphase (SEI) film on lithium metal anode that allows 400 cycles of Li/Li(NiMnCo)1/3O2 cells with a capacity retention of 97.0% at 0.83 mA cm-2. This work illustrates that low-cost fluorine-free carbonate solvents can also realize nonflammable electrolyte with high performance, which opens new opportunities to promote safety and energy density of rechargeable lithium batteries simultaneously.

Confined SnO2 quantum-dot clusters in graphene sheets as high-performance anodes for lithium-ion batteries.

Construction of metal oxide nanoparticles as anodes is of special interest for next-generation lithium-ion batteries. The main challenge lies in their rapid capacity fading caused by the structural degradation and instability of solid-electrolyte interphase (SEI) layer during charge/discharge process. Herein, we address these problems by constructing a novel-structured SnO2-based anode. The novel structure consists of mesoporous clusters of SnO2 quantum dots (SnO2 QDs), which are wrapped with reduced graphene oxide (RGO) sheets. The mesopores inside the clusters provide enough room for the expansion and contraction of SnO2 QDs during charge/discharge process while the integral structure of the clusters can be maintained. The wrapping RGO sheets act as electrolyte barrier and conductive reinforcement. When used as an anode, the resultant composite (MQDC-SnO2/RGO) shows an extremely high reversible capacity of 924 mAh g(-1) after 200 cycles at 100 mA g(-1), superior capacity retention (96%), and outstanding rate performance (505 mAh g(-1) after 1000 cycles at 1000 mA g(-1)). Importantly, the materials can be easily scaled up under mild conditions. Our findings pave a new way for the development of metal oxide towards enhanced lithium storage performance.