Conveying Advanced Li‐ion Battery Materials into Practice The Impact of Electrode Slurry Preparation Skills

Li‐ion batteries (LIB's) are of the greatest practical utility for portable electronics and electric vehicles (EV's). LIB energy, power and cycle life performances depend on cathode and anode compositions and morphology, electrolyte composition and the overall cell design. Electrode morphology is influenced by the shape and size of the active material (AM), conductive additive (CA) particles, the polymeric binder properties, and also on the AM/CA/binder mass ratio. At the same time, it also substantially depends on the electrode preparation process. This process is usually comprised of mixing a solvent, a binder, AM and CA powders, and casting the resulting slurry onto a current collector foil followed by a drying process. Whereas the problems of electrode morphology and their influence on the LIB‐electrode performance always receive a proper attention, the influence of slurry properties and slurry preparation techniques on the electrode morphology is often overlooked or at least underrated. The present work summarizes the current state‐of‐the‐art in the field of LIB‐electrode precursor slurries preparation, characterized by multicomponent compounds and large variations in sizes and shapes of the solid components. Approaches to LIB‐electrode slurry preparation are outlined and discussed in the context of the ultimate LIB‐electrode morphology and performance.     

Transition from Diffusion‐Controlled Intercalation into Extrinsically Pseudocapacitive Charge Storage of MoS2 by Nanoscale Heterostructuring

2D nanomaterials have been found to show surface‐dominant phenomena and understanding this behavior is crucial for establishing a relationship between a material's structure and its properties. Here, the transition of molybdenum disulfide (MoS₂) from a diffusion‐controlled intercalation to an emergent surface redox capacitive behavior is demonstrated. The ultrafast pseudocapacitive behavior of MoS₂ becomes more prominent when the layered MoS₂ is downscaled into nanometric sheets and hybridized with reduced graphene oxide (RGO). This extrinsic behavior of the 2D hybrid is promoted by the fast Faradaic charge‐transfer kinetics at the interface. The heterostructure of the 2D hybrid, as observed via high‐angle annular dark field–scanning transmission electron microscopy and Raman mapping, with a 1T MoS₂ phase at the interface and a 2H phase in the bulk is associated with the synergizing capacitive performance. This 1T phase is stabilized by the interactions with the RGO. These results provide fundamental insights into the surface effects of 2D hetero‐nanosheets on emergent electrochemical properties.     

Redox Shuttles with Axisymmetric Scaffold for Overcharge Protection of Lithium‐Ion Batteries

The derivatives of 1,4‐dimethoxybenzene are thus far the best performing redox shuttle additives for overcharge protection of Li‐ion batteries. The most durable molecules of this kind typically possess two in‐plane methoxy groups that are equivalent by inversion symmetry. However, such geometry leads to a vanishing average dipole moment that causes poor solubility of these molecules in carbonate‐based electrolytes. In this study, a novel redox shuttle additive, 1,2,3,4‐tetrahydro‐6,7‐dimethoxy‐1,1,4,4‐tetramethyl‐naphthalene (TDTN), is introduced. It has been demonstrated that reversible oxidation at 4.05 V versus Li⁺/Li, high polarity, high solubility (around 0.4 m ), and excellent electrochemical stability (150 overcharge cycles at C/2 rate with 100% overcharge) can all be achieved simultaneously by the imposition of axial symmetry in the corresponding radical cation that is generated by electrochemical oxidation of TDTN in the battery. The intricate interplay between the symmetry and the chemical stability of the radical cation is scrutinized using magnetic resonance spectroscopy and electron structure modeling.     

Two‐Dimensional Materials for Beyond‐Lithium‐Ion Batteries

Lithium‐ion batteries (LIBs) have dominated the portable electronics industry and solid‐state electrochemical research and development for the past two decades. In light of possible concerns over the cost and future availability of lithium, sodium‐ion batteries (SIBs) and other new technologies have emerged as candidates for large‐scale stationary energy storage. Research in these technologies has increased dramatically with a focus on the development of new materials for both the positive and negative electrodes that can enhance the cycling stability, rate capability, and energy density. Two‐dimensional (2D) materials are showing promise for many energy‐related applications and particularly for energy storage, because of the efficient ion transport between the layers and the large surface areas available for improved ion adsorption and faster surface redox reactions. Recent research highlights on the use of 2D materials in these future ‘beyond‐lithium‐ion’ battery systems are reviewed, and strategies to address challenges are discussed as well as their prospects.     

Xylene‐Bridged Phosphaviologen Oligomers and Polymers as High‐Performance Electrode‐Modifiers for Li‐Ion Batteries

Lithium‐ion batteries are one of the most common forms of energy storage devices used in society today. Due to the inherent limitations of conventional Li‐ion batteries, organic materials have surfaced as potentially suitable electrode alternatives with improved performance and sustainability. Viologens and phosphaviologens in particular, are strong electron‐accepting materials with excellent kinetic properties, making them suitable candidates for battery applications. In this paper, new polymeric species of the latter moieties are reported that lead to improved electrode stability and device performance. The performance of the phosphaviologen is further enhanced through the utilization of both redox steps, allowing for good performance proof‐of‐concept hybrid organic/Li‐ion batteries. This opens the potential for more sustainable and improved battery performance for use in current energy applications.     

3D Vertically Aligned and Interconnected Porous Carbon Nanosheets as Sulfur Immobilizers for High Performance Lithium‐Sulfur Batteries

A unique nanostructure of 3D and vertically aligned and interconnected porous carbon nanosheets (3D‐VCNs) is demonstrated by a simple carbonization of agar. The key feature of 3D‐VCNs is that they possess numerous 3D channels with macrovoids and mesopores, leading to high surface area of 1750 m² g^?1, which play an important role in loading large amount of sulfur, while vertically aligned microporous carbon nanosheets act as the multilayered physical barrier against polysulfides anions and prevent their dissolution in the electrolyte due to strong adsorption during cycling process. As a result, the 3D hybrid (3D‐S‐VCNs) infiltered with 68.3 wt% sulfur exhibits a high and stable reversible capacity of 844 mAh g^?1 at the current density of 837 mA g^?1 with excellent Coulombic efficiency ≈100%, capacity retention of ≈80.3% over 300 cycles, and good rate ability (the reversible capacity of 738 mAh g^?1 at the high current density of 3340 mA g^?1). The present work highlights the vital role of the introduction of 3D carbon nanosheets with macrovoids and mesopores in enhancing the performance of LSBs.     

Single‐Ion Conducting Electrolyte Based on Electrospun Nanofibers for High‐Performance Lithium Batteries

Herein, a novel electrospun single‐ion conducting polymer electrolyte (SIPE) composed of nanoscale mixed poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) and lithium poly(4,4′‐diaminodiphenylsulfone, bis(4‐carbonyl benzene sulfonyl)imide) (LiPSI) is reported, which simultaneously overcomes the drawbacks of the polyolefin‐based separator (low porosity and poor electrolyte wettability and thermal dimensional stability) and the LiPF₆ salt (poor thermal stability and moisture sensitivity). The electrospun nanofiber membrane (es‐PVPSI) has high porosity and appropriate mechanical strength. The fully aromatic polyamide backbone enables high thermal dimensional stability of es‐PVPSI membrane even at 300 °C, while the high polarity and high porosity ensures fast electrolyte wetting. Impregnation of the membrane with the ethylene carbonate (EC)/dimethyl carbonate (DMC) (v:v = 1:1) solvent mixture yields a SIPE offering wide electrochemical stability, good ionic conductivity, and high lithium‐ion transference number. Based on the above‐mentioned merits, Li/LiFePO₄ cells using such a SIPE exhibit excellent rate capacity and outstanding electrochemical stability for 1000 cycles at least, indicating that such an electrolyte can replace the conventional liquid electrolyte–polyolefin combination in lithium ion batteries (LIBs). In addition, the long‐term stripping–plating cycling test coupled with scanning electron microscope (SEM) images of lithium foil clearly confirms that the es‐PVPSI membrane is capable of suppressing lithium dendrite growth, which is fundamental for its use in high‐energy Li metal batteries.