Electrolyte Strategies Facilitating Anion-Derived Solid-Electrolyte Interphases for Aqueous Zinc-Metal Batteries.

Rechargeable aqueous zinc-metal batteries (AZBs) are a promising complimentary technology to the existing lithium-ion batteries and the re-emerging lithium-metal batteries to satisfy the increasing demands on energy storage. Despite considerable progress achieved in the past years, the fundamental understanding of the solid-electrolyte interphase (SEI) formation and how its composition influences the SEI properties are limited. This review highlights the functionalities of anion-tuned SEI on the reversibility of zinc-metal anode, with a specific emphasis on new structural insights obtained through advanced characterizations and computational techniques. Recent efforts in terms of key variables that govern the interfacial behaviors to improve the long-term stability of zinc anode, i.e., Coulombic efficiency, plating morphology, dendrite formation, and side-reactions, are comprehensively reviewed. Lastly, the remaining challenges and future perspectives are presented, providing insights into the rational design of practical high-performance AZBs.

Interfacial "Single-Atom-in-Defects" Catalysts Accelerating Li+ Desolvation Kinetics for Long-Lifespan Lithium-Metal Batteries.

The lithium-metal anode is a promising candidate for realizing high-energy-density batteries owing to its high capacity and low potential. However, several rate-limiting kinetic obstacles, such as the desolvation of Li+ solvation structure to liberate Li+ , Li0 nucleation, and atom diffusion, cause heterogeneous spatial Li-ion distribution and fractal plating morphology with dendrite formation, leading to low Coulombic efficiency and depressive electrochemical stability. Herein, differing from pore sieving effect or electrolyte engineering, atomic iron anchors to cation vacancy-rich Co1- x S embedded in 3D porous carbon (SAFe/CVRCS@3DPC) is proposed and demonstrated as catalytic kinetic promoters. Numerous free Li ions are electrocatalytically dissociated from the Li+ solvation complex structure for uniform lateral diffusion by reducing desolvation and diffusion barriers via SAFe/CVRCS@3DPC, realizing smooth dendrite-free Li morphologies, as comprehensively understood by combined in situ/ex situ characterizations. Encouraged by SAFe/CVRCS@3DPC catalytic promotor, the modified Li-metal anodes achieve smooth plating with a long lifespan (1600 h) and high Coulombic efficiency without any dendrite formation. Paired with the LiFePO4 cathode, the full cell (10.7 mg cm-2 ) stabilizes a capacity retention of 90.3% after 300 cycles at 0.5 C, signifying the feasibility of using interfacial catalysts for modulating Li behaviors toward practical applications.

Bioactivity of the cannabigerol cannabinoid and its analogues - the role of 3-dimensional conformation.

Cannabinoids are naturally occurring bioactive compounds with the potential to help treat chronic illnesses including epilepsy, Parkinson's disease, dementia and multiple sclerosis. Their general structures and efficient syntheses are well documented in the literature, yet their quantitative structure-activity relationships (QSARs), particularly 3-dimensional (3-D) conformation-specific bioactivities, are not fully resolved. Cannabigerol (CBG), an antibacterial precursor molecule for the most abundant phytocannabinoids, was characterised herein using density functional theory (DFT), together with selected analogues, to ascertain the influence of the 3D structure on their activity and stability. Results showed that the CBG family's geranyl chains tend to coil around the central phenol ring while its alkyl side-chains form H-bonds with the para-substituted hydroxyl groups as well as CH⋯π interactions with the aromatic density of the ring itself, among other interactions. Although weakly polar, these interactions are structurally and dynamically influential, effectively 'stapling' the ends of the chains to the central ring structure. Molecular docking of the differing 3-D poses of CBG to cytochrome P450 3A4 resulted in lowered inhibitory action by the coiled conformers, relative to their fully-extended counterparts, helping explain the trends in the inhibition of the metabolic activity of the CYP450 3A4. The approach detailed herein represents an effective method for the characterisation of other bioactive molecules, towards improved understanding of their QSARs and in guiding the rational design and synthesis of related compounds.

Locally Concentrated Ionic Liquid Electrolytes for Lithium-Metal Batteries.

Non-flammable ionic liquid electrolytes (ILEs) are well-known candidates for safer and long-lifespan lithium metal batteries (LMBs). However, the high viscosity and insufficient Li+ transport limit their practical application. Recently, non-solvating and low-viscosity co-solvents diluting ILEs without affecting the local Li+ solvation structure are employed to solve these problems. The diluted electrolytes, i.e., locally concentrated ionic liquid electrolytes (LCILEs), exhibiting lower viscosity, faster Li+ transport, and enhanced compatibility toward lithium metal anodes, are feasible options for the next-generation high-energy-density LMBs. Herein, the progress of the recently developed LCILEs are summarised, including their physicochemical properties, solution structures, and applications in LMBs with a variety of high-energy cathode materials. Lastly, a perspective on the future research directions of LCILEs to further understanding and achieve improved cell performances is outlined.

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

Lithium metal anodes are ideal for realizing high-energy-density batteries owing to their advantages, namely high capacity and low reduction potentials. However, the utilization of lithium anodes is restricted by the detrimental lithium dendrite formation, repeated formation and fracturing of the solid electrolyte interphase (SEI), and large volume expansion, resulting in severe "dead lithium" and subsequent short circuiting. Currently, the researches are principally focused on inhibition of dendrite formation toward extending and maintaining battery lifespans. Herein, we summarize the strategies employed in interfacial engineering and current-collector host designs as well as the emerging electrochemical catalytic methods for evolving-accelerating-ameliorating lithium ion/atom diffusion processes. First, strategies based on the fabrication of robust SEIs are reviewed from the aspects of compositional constituents including inorganic, organic, and hybrid SEI layers derived from electrolyte additives or artificial pretreatments. Second, the summary and discussion are presented for metallic and carbon-based three-dimensional current collectors serving as lithium hosts, including their functionality in decreasing local deposition current density and the effect of introducing lithiophilic sites. Third, we assess the recent advances in exploring alloy compounds and atomic metal catalysts to accelerate the lateral lithium ion/atom diffusion kinetics to average the spatial lithium distribution for smooth plating. Finally, the opportunities and challenges of metallic lithium anodes are presented, providing insights into the modulation of diffusion kinetics toward achieving dendrite-free lithium metal batteries.

Production of high-energy Li-ion batteries comprising silicon-containing anodes and insertion-type cathodes.

Rechargeable Li-based battery technologies utilising silicon, silicon-based, and Si-derivative anodes coupled with high-capacity/high-voltage insertion-type cathodes have reaped significant interest from both academic and industrial sectors. This stems from their practically achievable energy density, offering a new avenue towards the mass-market adoption of electric vehicles and renewable energy sources. Nevertheless, such high-energy systems are limited by their complex chemistry and intrinsic drawbacks. From this perspective, we present the progress, current status, prevailing challenges and mitigating strategies of Li-based battery systems comprising silicon-containing anodes and insertion-type cathodes. This is accompanied by an assessment of their potential to meet the targets for evolving volume- and weight-sensitive applications such as electro-mobility.

CO2 Capture in Ionic Liquids Based on Amino Acid Anions With Protic Side Chains: a Computational Assessment of Kinetically Efficient Reaction Mechanisms.

Absorption and capture of CO2 directly from sources represents one of the major tools to reduce its emission in the troposphere. One of the possibilities is to incorporate CO2 inside a liquid exploiting its propensity to react with amino groups to yield carbamic acid or carbamates. A particular class of ionic liquids, based on amino acids, appear to represent a possible efficient medium for CO2 capture because, at difference with current industrial setups, they have the appeal of a biocompatible and environmentally benign solution. We have investigated, by means of highly accurate computations, the feasibility of the reaction that incorporates CO2 in an amino acid anion with a protic side chain and ultimately transforms it into a carbamate derivative. Through an extensive exploration of the possible reaction mechanisms, we have found that different prototypes of amino acid anions present barrierless reaction mechanisms toward CO2 absorption.

Ab Initio Molecular Dynamics Study of Phospho-Amino Acid-Based Ionic Liquids: Formation of Zwitterionic Anions in the Presence of Acidic Side Chains.

We present a computational analysis of the complex proton-transfer processes in two protic ionic liquids based on phosphorylated amino acid anions. The structure and the short time dynamics have been analyzed via ab initio and semi-empirical molecular dynamics. Given the presence of mobile protons on the side chain, such ionic liquids may represent a viable prototype of highly conductive ionic mediums. The results of our simulations are not entirely satisfactory in this respect. Our results indicate that conduction in these liquids may be limited due to a quick quenching of the proton-transfer processes. In particular, we have found that, while proton migration does occur on very short timescales, the amino groups act as proton scavengers preventing an efficient proton migration. Despite their limits as conductive mediums, we show that these ionic liquids possess an unconventional microscopic structure, where the anionic component is made by amino acid anions that the aforementioned proton transfer has transformed into zwitterionic isomers. This unusual chemical structure is relevant because of the recent use of amino acid-based ionic liquids, such as CO2 absorbent.

Structural Features of Cholinium Based Protic Ionic Liquids through Molecular Dynamics.

An analysis of the complex proton transfer processes in certain protic ionic liquids, based on amino acid anions, has been carried out through ab initio molecular dynamics in the view of finding naturally conductive and pure mediums. The systems analyzed here might serve as chemical prototypes for pure and dry ionic liquids where mobile protons can act as fast charge carriers. We have exploited the natural tendency of these liquids to form a complex network of hydrogen bonds. The presence of such a network allows the naturally repulsive interaction between like charge ions to be weakened to the point that a proton migration process inside the anionic component of the fluid becomes possible. We have also seen that the extent of these proton migrations is sizable for carboxylic based amino acid anions, while it is very limited for sulfur containing ones.

Hydrogen Bonding as a Clustering Agent in Protic Ionic Liquids: Like-Charge vs Opposite-Charge Dimer Formation.

The local structure of a series of homologous protic ionic liquids (PILs) is investigated using ab initio computations and ab initio-based molecular dynamics. The purpose of this work is to show that in PILs the network of hydrogen bonds may promote like-charge clustering between anionic species. We correlate the theoretical evidence of this possibility with viscosity experimental data. The homologous series of liquids is obtained by coupling choline with amino acid anions and varying the side chain. We find that the frictional properties of the liquids are clearly connected to the ability of the side chain to establish additional hydrogen bonds (other than the trivial cation-anion interaction). We also show that the large variation of bulk properties along the series of compounds can be explained by assuming that one of the sources of friction in the bulk liquid is the like-charge interaction between anions.