Search Results (54)

Ionic liquid-based localized high-concentration electrolytes, leveraging their intrinsically nonflammable safety characteristics and wide electrochemical windows, have emerged as strong contenders for next-generation lithium metal battery electrolytes. However, because such systems are anion-rich, the electrolyte bulk phase tends to form solvation structures dominated by bulky anionic clusters along with an excess of free anions, which triggers persistent and uncontrollable anion decomposition at the interphase. To address this issue, we adopt a strategy of constructing a compressed solvation structure by introducing a weakly interacting chlorinated diluent (TeCA), which helps form a compact solvation environment and alleviates excessive anion decomposition at electrode interphases. In this work, 1,1,2,2-tetrachloroethyl acetate (TeCA) was introduced as a weakly coordinating chlorinated diluent into an ionic-liquid localized high-concentration electrolyte (LHCE) to regulate the Li⁺-FSI⁻ solvation environment. By combining Raman spectroscopy, molecular dynamics simulations, and electrochemical characterization, the TeCA-LHCE system was found to exhibit altered ion-cluster configurations, improved oxidation tolerance, and enhanced interfacial stability under high-voltage conditions. The as-prepared TeCA-LHCE electrolyte presents improved electrochemical performance in comparison with TTE-LHCE and the baseline electrolyte (BE). The Li||Cu half-cell employing TeCA-LHCE achieved a high Coulombic efficiency above 99% over 500 cycles and formed a uniform and dense lithium deposition layer without obvious dendritic growth. When paired with a high-loading NCM811 cathode (10 mg cm⁻²), the TeCA-LHCE-based Li||NCM811 full cell delivered significantly improved cycling stability and rate capability under a high cutoff voltage of 4.3 V. Full article

Protein phosphatase PPM1A plays a critical role in cellular signaling by dephosphorylating key regulatory proteins. According to experimental data, the enzyme requires either Mn²⁺ or Mg²⁺ bound in the active center(s), hence its catalytic activity strongly depends on the chelated metal ions. In this study, the metal ion selectivity of PPM1A is investigated using DFT calculations on active site constructs of bi- and trinuclear metal centers and protein ligands from the first and second metal coordination shells. Binuclear Mn-Mn and trinuclear Mn-Mn-Mn sites show poor resistance to substitution by biogenic Fe²⁺ and Zn²⁺, with Gibbs energies of the Mn²⁺ → Fe²⁺/Zn²⁺ exchange being consistently negative in both the gas phase and condensed media. In contrast, Mg-Mg and Mg-Mg-Mg centers are substantially more robust, with a thermodynamically unfavorable Mg²⁺ → Fe²⁺/Zn²⁺ substitution—except in the case of the Mg-Mg-Zn complex. The primary factors governing this metal competition in the modeled structures are the nature of the competing cation and the solvation properties of its aqua complexes, while solvent exposure of the binding site and the number of metal cations in the catalytic center exert a comparatively minor effect. Overall, these findings demonstrate that Mg²⁺-loaded active sites offer considerably greater protection against biogenic metal displacement than their Mn²⁺ counterparts, thus shedding light on the metalloprotein stability and enzyme fidelity of PPM1A. Full article

Histone deacetylase inhibitors (HDACi) are an emerging class of epigenetic anticancer drugs that exert their activity through coordination to the catalytic Zn²⁺ ion within the active site of histone deacetylases (HDACs). Due to the limited isoform-selectivity of hydroxamic acid-based inhibitors, benzamide-based HDACi (BBHDACi) have been developed as subtype-selective alternatives. Clinically relevant representatives include Chidamide, Entinostat, Mocetinostat, Zabadinostat, and Tacedinaline. Although these compounds share a conserved o-aminoanilide zinc-binding group (ZBG), they differ in linker and cap region structure, raising questions regarding their intrinsic Zn²⁺ affinity and coordination behavior. Herein, density functional theory (DFT) calculations were performed at the B3LYP/6-311++g(d,p) level of theory combined with the PCM solvation in methanol (ε = 33) and water (ε = 78). Geometry optimization confirmed that the trans (E) isomer of Chidamide is thermodynamically preferred. Coordination studies showed that the remaining BBHDACi adopt stable geometries, with the o-aminoanilide group preferentially forming tetracoordinated complexes that are more stable than hexacoordinated ones in polar media. Interestingly, calculated substitution free energies differed by less than ± 2 kcal.mol⁻¹, indicating nearly identical intrinsic Zn²⁺ affinities across the series. These results suggest that the ZBG contributes similarly to metal coordination across all BBHDACi, whereas the overall binding strength is mainly governed by interactions of the linker and cap regions rather than by the conserved zinc-binding group itself. Full article

The demand for high-energy-density and fast-charging solid-state lithium metal batteries (SSLMBs) often subjects practical devices to internal thermal loads, making high-temperature operation a common operational condition rather than an isolated scenario. To address the interfacial degradation and dendrite growth accelerated by such thermomechanical stresses, we developed a composite gel electrolyte (CGE) by incorporating an optimal concentration of active Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO) into a fluoropolymer network. The abundant Lewis acidic sites on the LLZTO surfaces promote competitive solvation decoupling by interacting with anions, thereby modulating the primary solvation sheath of Li⁺. This localized modulation lowers the lithium-ion migration activation energy to 0.248 eV and facilitates a dual-interfacial passivation mechanism. Specifically, a rigid, inorganic-rich solid electrolyte interphase (SEI) forms to suppress morphological instability at the lithium anode, while an organic-dominated cathode electrolyte interphase (CEI) enhances the oxidative stability up to 4.3 V. As a result, symmetric cells demonstrate stable electrodeposition for over 450 h at 80 °C and 0.5 mA cm⁻². Furthermore, NCM811/Li full cells utilizing this CGEs exhibit significantly improved thermal resilience and cycling stability. Full article

Human serum albumin (HSA) is one of the main proteins in human blood plasma and serves as a molecular “taxi” transporting various compounds, including organic compounds, drugs, metal ions, etc., through the circulatory system throughout the human body. As with any other proteins, HSA hydration plays an important role in maintaining its structure and functioning as well as influencing its ability to bind to ligands. This contribution presents, for the first time, a generalized picture of hydration of this biomacromolecule obtained within the framework of the 3D-RISM (three-dimensional Reference Interaction Site Model) theory of solvation. Based on 3D isodensity maps and structural parameters (hydration numbers, hydration layer thickness, fraction of hydrogen bonds, SASA, etc.), the most probable model of HSA hydration structure was reconstructed. With the description of HSA hydration, two important issues were also addressed in detail. The first is the correct determination of the hydration layer thickness, a common problem in protein science. The second is the possible state and behavior of hydration water in HSA–ligand binding. The presented results provide a deeper understanding of the relationship between solvent and HSA, which brings new knowledge to the understanding of protein hydration. Full article

The increasing demand for sustainable and high-performance energy storage underscores the limitations of lithium-ion batteries (LIBs), notably in terms of finite resources, safety issues, and rising costs. Multivalent metal-ion batteries (MMIBs)—employing Zn²⁺, Mg²⁺, Ca²⁺, and Al³⁺ ions—represent promising alternatives, as their multivalent charge carriers facilitate higher energy densities and greater electron transfer per ion. The widespread availability, lower cost, and favorable safety profiles of these metals further enhance MMIB suitability for large-scale deployment. However, MMIBs encounter significant obstacles, including slow ion diffusion, strong Coulombic interactions, electrolyte instability, and challenging interfacial compatibility. This review provides a systematic overview of recent advancements in MMIB research. Key developments are discussed for each system: electrode synthesis and flexible architectures for zinc-ion batteries; anode and cathode innovation alongside electrolyte optimization for magnesium-ion systems; improvements in anode engineering and solvation strategies for calcium-ion batteries; and progress in electrolyte formulation and cathode design for aluminum-ion batteries. The review concludes by identifying persistent challenges and future directions, with particular attention to material innovation, electrolyte chemistry, interfacial engineering, and the adoption of data-driven approaches, thereby informing the advancement of next-generation MMIB technologies. Full article

This study used density functional theory (DFT)-based first-principles calculations to investigate the desolvation effect of single-walled carbon nanotubes (SWCNTs) modified with hydroxyl (-OH), carbonyl (-C=O), and carboxyl (-COOH) groups. SWCNTs have great potential as supercapacitor electrode materials due to their unique structural and electronic properties, but their practical application is limited by poor solvation-induced dispersibility and low ion transport efficiency. To solve this, this study constructed functionalized SWCNT models, simulated their interaction with lithium ion (Li⁺) complexes in acetonitrile (AN) solvent, and analyzed Li⁺ desolvation behavior, relative capacitance, and post-desolvation density of states (DOSs). The key research results are as follows: [Li(AN)]⁺ complete desolvation sizes differed: 5.91 Å (pristine SWCNTs), 6.26 Å (hydroxylated SWCNTs, HCNT), 6.11 Å (carbonylated SWCNTs, CNCNT; carboxylated SWCNTs, CXCNT). HCNT showed the largest relative capacitance enhancement (max 1.4× pristine), while CNCNT and CXCNT both had a max 1.3× improvement. Post-desolvation DOS analysis revealed distinct electronic property changes: HCNT-Li⁺ enhanced metallicity and conductivity; CNCNT-Li⁺ increased metallicity but reduced conductivity; and CXCNT-Li⁺ decreased metallicity with nearly unchanged conductivity. This study provides an atomic-scale theoretical basis for optimizing the properties of SWCNT solutions, supporting their application in high-performance supercapacitors, particularly in enhancing device energy density and cycle stability. Full article

The structures of hexaammine solvated indium(III) and thallium(III) ions in liquid ammonia solution are determined by EXAFS. Both complexes have regular octahedral coordination geometry with mean In-N and Tl-N bond distances of 2.23(1) and 2.29(2) Å, respectively. Ammine solvated thallium(III) in liquid ammonia is characterized with ²⁰⁵Tl NMR measurements. Solvents such as liquid ammonia, N,N-dimethylthioformamide (DMTF), trialkyl and triphenyl phosphite and phosphine are strong electron pair donors and thereby able to form bonds with a large covalent contribution with strong electron pair acceptors. A survey of reported structures of ammine, DMTF, trialkyl and triphenyl phosphite and phosphine solvated metal ions in the solid state and solution is presented. The M-N and M-S bond distances in ammine and DMTF solvated metal ions are compared with the M-O bond distance in the corresponding metal ion hydrates, expected to form mainly electrostatic interactions with metal ions. The d¹⁰ metal ions have high ability to form bonds with a high degree of covalency with increasing ability down the group and with decreasing charge of the metal ion. The difference in M-N and M-O bond distances between ammine solvated and hydrated metal ions with the same coordination geometry decreases significantly with the increasing ability of the metal ion to form bonds with a large covalent contribution. This difference correlates well with the covalent bonding index, γ_M²*r. Full article

Polymer electrolytes (PEs) provide enhanced safety for high–energy–density lithium metal batteries (LMBs), yet their practical application is hampered by intrinsically low ionic conductivity and insufficient electrochemical stability, primarily stemming from suboptimal Li⁺ solvation environments and transport pathways coupled with slow polymer dynamics. Herein, we demonstrate a molecular design strategy to overcome these limitations by regulating the Li⁺ solvation structure through the synergistic interplay of conventional Lewis acid–base coordination and engineered hydrogen bond (H–bond) networks, achieved by incorporating specific H–bond donor functionalities (N,N′–methylenebis(acrylamide), MBA) into the polymer architecture. Computational modeling confirms that the introduced H–bonds effectively modulate the Li⁺ coordination environment, promote salt dissociation, and create favorable pathways for faster ion transport decoupled from polymer chain motion. Experimentally, the resultant polymer electrolyte (MFE, based on MBA) enables exceptionally stable Li metal cycling in symmetric cells (>4000 h at 0.1 mA cm⁻²), endows LFP|MFE|Li cells with long–term stability, achieving 81.0% capacity retention after 1400 cycles, and confers NCM622|MFE|Li cells with cycling endurance, maintaining 81.0% capacity retention after 800 cycles under a high voltage of 4.3 V at room temperature. This study underscores a potent molecular engineering strategy, leveraging synergistic hydrogen bonding and Lewis acid–base interactions to rationally tailor the Li⁺ solvation structure and unlock efficient ion transport in polymer electrolytes, paving a promising path towards high–performance solid–state lithium metal batteries. Full article

It has been demonstrated that the traditional hydrometallurgical method is still economically viable in several industrial applications such as Bayer, Boix, Platsol, Sherrit-Gordon, and so on. The conventional extraction technique of valuable metals from their ores using an aqua medium has several challenges. The following can be listed for the illustration of this: (1) Inorganic acids used during the leaching process have been proven to be non-environmentally friendly and ready to lead to non-selective processes in general, except in rare cases used in alkaline environments. (2) Special linings are required in the reactors used due to the corrosive impact of acids such as HCl and H₂SO_4, especially when leaching at high temperatures, rendering all processes costly. (3) Practically, using inorganic acids while leaching samples containing amorphous silicate phases leads to gel formation. Solvometallurgy overcomes these challenges by substituting the aqueous phase for other polar solvents, such as polar molecular organic or ionic solvents. The advantage of this substitution lies in the ability to manipulate metal ion distribution using solvents with varying solvation properties. This review examines the potential of solvometallurgical processes (solvoleaching) over conventional hydrometallurgy as viable alternatives for metal extraction from sulfide ores. It highlights the key distinctions between hydrometallurgy and solvometallurgy while emphasizing the potential economic and environmental advantages solvometallurgy offers. Full article

The formation of unstable solid electrolyte interphases (SEIs) on the surface of lithium metal anodes poses a significant barrier to the commercialization of lithium metal batteries (LMBs). Rational modulation of solvation structures within the electrolytes emerged as one of the most effective strategies to enhance interfacial stability in LMBs; however, this approach often compromises the structural stability of the bulk electrolyte. Herein, we present an innovative method that improves interface stability without adversely affecting the bulk electrolyte’s structural stability. By employing ZSM molecular sieves as efficient ion channels on the lithium metal anode surface—termed ZSM electrolytes—a more aggregated solvation structure is induced at the lithium metal interface, resulting in an anion-rich interphase. This anion-enriched environment promotes the formation of an SEI derived from anions, thereby enhancing the stability of the lithium metal interface. Consequently, Li||Cu cells utilizing the ZSM electrolyte achieve an average coulombic efficiency (CE) of 98.76% over 700 h. Moreover, LiFePO₄||Li batteries exhibit stable cycling performance exceeding 900 cycles at a current density of 1 C. This design strategy offers robust support for effective interfacial regulation in lithium metal batteries. Full article

This study investigates the effects of common additives, which provide distinct proton sources—ammonium (NH₄⁺) and hydronium (H₃O⁺)—along with their corresponding conjugate base species, on signal intensity in positive ionization mode. The findings reveal that signal intensity is influenced by factors such as solvation enthalpy, surface tension, and conductivity. At lower additive concentrations (<10 mM), based on fold changes, no clear distinction could be made between formic acid, acetic acid, and their corresponding salts. At higher additive concentrations, NH₄⁺ appears to be a more efficient proton source than H⁺ (H₃O⁺), likely due to its more positive solvation enthalpy, which promotes greater enrichment of NH₄⁺ on the droplet surface, as well as the reduced surface tension of ammonium salts compared to their acid counterparts. Additionally, ammonium hydroxide proves to be the most effective ammonium-based modifier, likely due to its anionic conjugate base, hydroxide, which has a more negative solvation enthalpy compared to acetate and formate. This characteristic is hypothesized to reduce charge neutralization of cations on the droplet surface and/or in the gas phase. Furthermore, ammonium hydroxide exhibits lower conductivity compared to the other ammonium additives, which is believed to enhance signal intensity. Ammonium bicarbonate, the second most effective additive, uniquely prevents metal adduct formation, leading to enhanced [M + H]⁺ ion signals. Full article

Electrolytes play a vital role in the performance and safety of electrochemical energy storage devices, such as lithium-ion batteries (LIBs). While traditional LIBs rely on organic electrolytes, these flammable solutions pose safety risks and require expensive, moisture-sensitive manufacturing processes. Aqueous electrolytes offer a safer, more cost-effective alternative, but their narrow electrochemical window, corrosivity to electrodes, and enabling of dendritic growth on metal anodes limit their practical applications. Water-in-salt electrolytes (WiSEs) have emerged as a promising solution to these challenges. By significantly reducing water activity and forming a stable solid–electrolyte interphase (SEI), WiSEs can expand the electrochemical stability window, inhibit material dissolution, and suppress dendritic growth. This unique SEI formation mechanism, which is similar to that observed in organic electrolytes, contributes to the improved performance and stability of WiSE-based batteries. Additionally, the altered solvation structure of WiSEs minimizes the presence of free water molecules, further stabilizing the SEI and reducing water activity. This review comprehensively examines the composition, mechanisms, and characterization of WiSEs and their application in monovalent-metal-ion batteries. Full article

Data on the diffusion and migration characteristics of rare earth metal ions in fluoride molten salt systems are crucial for optimizing the electrolytic preparation of rare earth metals and alloys. This study investigated the solubility, conductivity, and density of the (LiF-CaF₂)_eut. system saturated with Nd₂O₃ using the isothermal saturation method, conductivity cell constant variation, and the Archimedes method, respectively. Employing the Hittorf method’s principles, a three-compartment electrolyzer was designed to determine the mobility number of dissolved Nd* (III) ions in the saturated (LiF-CaF₂)_eut.-Nd₂O₃ system. The radial distribution function was computed via ab initio molecular dynamics, and the self-diffusion coefficient of ions in the system was analyzed. Utilizing the Nernst–Einstein equation, the diffusion coefficient of Nd* (III) ions was calculated. The solubility, conductivity, and density of the saturated (LiF-CaF₂)_eut.-Nd₂O₃ system exhibit linear variation within 1173–1473 K. The mobility number of solvated Nd* (III) ions increases linearly with temperature, displaying nonlinear variation with potential within 3.5–4.5 V, and gradually decreases after reaching a maximum of 4.0–4.25 V. The radial distribution function reveals the highest diffusion and mobility barriers for Nd* (III) ions, with solvated O* (II) ions presenting the most significant hindrance. The Nd* (III) ion diffusion coefficients linearly increase with temperature (1123–1373 K) under specific potential conditions (3.5–4.5 V) but exhibit nonlinear changes with potential (3.5–4.5 V) under fixed temperature conditions (1123–1373 K), then decrease after peaking within 4.0–4.5 V. The diffusion coefficients of Nd* (III) ions are sensitive to potential changes. Full article

Lithium metal batteries (LiMBs) have emerged as extremely viable options for next-generation energy storage owing to their elevated energy density and improved theoretical specific capacity relative to traditional lithium batteries. However, safety concerns, such as the flammability of organic liquid electrolytes, have limited their extensive application. In the present study, we utilize molecular dynamics and Density Functional Theory based simulations to investigate the Li interactions in gel polymer electrolytes (GPEs), composed of a 3D cross-linked polymer matrix combined with two different non-flammable electrolytes: 1 M lithium hexafluorophosphate (LiPF₆) in ethylene carbonate (EC)/dimethyl carbonate (DMC) and 1 M lithium bis(fluorosulfonyl)imide (LiFSI) in trimethyl phosphate (TMP) solvents. The findings derived from radial distribution functions, coordination numbers, and interaction energy calculations indicate that Li⁺ exhibits an affinity with solvent molecules and counter-anions over the functional groups on the polymer matrix, highlighting the preeminent influence of electrolyte components in Li⁺ solvation and transport. Furthermore, the second electrolyte demonstrated enhanced binding energies, implying greater ionic stability and conductivity relative to the first system. These findings offer insights into the Li⁺ transport mechanism at the molecular scale in the GPE by suggesting that lithium-ion transport does not occur by hopping between polymer functional groups but by diffusion into the solvent/counter anion system. The information provided in the work allows for the improvement of the design of electrolytes in LiMBs to augment both safety and efficiency. Full article