Rechargeable Dual‐Ion Batteries with Graphite as a Cathode: Key Challenges and Opportunities

Rechargeable graphite dual‐ion batteries (GDIBs) have attracted the attention of electrochemists and material scientists in recent years due to their low cost and high‐performance metrics, such as high power density (≈3–175 kW kg^?1), energy efficiency (≈80–90%), long cycling life, and high energy density (up to 200 Wh kg^?1), suited for grid‐level stationary storage of electricity. The key feature of GDIBs is the exploitation of the reversible oxidation of the graphite network with concomitant and highly efficient intercalation/deintercalation of bulky anionic species between graphene layers. In this review, historical and current research aspects of GDIBs are discussed, along with key challenges in their development and practical deployment. Specific emphasis is given to the operational mechanism of GDIBs and to unbiased and correct reporting of theoretical cell‐level energy densities.     

Strong Interplay between Sodium and Oxygen in Kesterite Absorbers: Complex Formation,Incorporation, and Tailoring Depth Distributions

Sodium and oxygen are prevalent impurities in kesterite solar cells. Both elements are known to strongly impact performance of the kesterite devices and can be connected to efficiency improvements seen after heat treatments. The sodium distribution in the kesterite absorber is commonly reported, whereas the oxygen distribution has received less attention. Here, a direct relationship between sodium and oxygen in kesterite absorbers is established using secondary ion mass spectrometry and explained by defect analyses within the density functional theory. The calculations reveal a binding energy of 0.76 eV between the substitutional defects Na_Cu and O_S in the nearest neighbor configuration, indicating an abundance of Na? O complexes in kesterite absorbers at relevant temperatures. Oxygen incorporation is studied by introducing isotopic ¹⁸O at different stages of the Cu₂ZnSnS₄/Mo/soda‐lime glass baseline processing. It is observed that oxygen from the Mo back contact and contaminations during the sulfurization are primary contributors to the oxygen distribution. Indeed, unintentional oxygen incorporation leads to immobilization of sodium. This results in a strong correlation between sodium and oxygen, in excellent agreement with the theoretical calculations. Consequently, oxygen availability should be monitored to optimize postdeposition heat treatments to control impurities in kesterite absorbers and ultimately, the solar cell efficiency.     

Insights into the Effects of Electrolyte Composition on the Performance and Stability of FeF2 Conversion‐Type Cathodes

As an alternative to commercial Ni‐ and Co‐based intercalation‐type cathode materials, conversion‐type metal fluoride (MF_x) cathodes are attracting more interest due to their promises to increase cell‐level energy density when coupled with lithium (Li) or silicon (Si)‐based anodes. Among metal fluorides, iron fluorides (FeF₂ and FeF₃) are regarded as some of the most promising candidates due to their high capacity, moderately high potential and the very low cost of Fe. In this study, the impacts of electrolyte composition on the performance and stability of nanostructured FeF₂ cathodes are systematically investigated. Dramatic impacts of Li salt composition, Li salt concentration, solvent composition, and cycling potential range on the cathode's most critical performance parameters—stability, capacity, rate, and voltage hysteresis are discovered. In contrast to previous beliefs, it is observed that even if the Fe²⁺ cation dissolution could be avoided, the dissolution of F^? anions may still negatively affect cathode performance. Formation of the more favorable cathode solid electrolyte interface (CEI) is found to minimize both processes.     

Understanding Li‐Ion Dynamics in Lithium Hydroxychloride (Li2OHCl) Solid State Electrolyte via Addressing the Role of Protons

Low‐melting‐point solid‐state electrolytes (SSE) are critically important for low‐cost manufacturing of all‐solid‐state batteries. Lithium hydroxychloride (Li₂OHCl) is a promising material within the SSE domain due to its low melting point (mp < 300 °C), cheap ingredients (Li, H, O, and Cl), and rapid synthesis. Another unique feature of this compound is the presence of Li vacancies and rotating hydroxyl groups which promote Li‐ion diffusion, yet the role of the protons in the ion transport remains poorly understood. To examine lithium and proton dynamics, a set of solid‐state NMR experiments are conducted, such as magic‐angle spinning ⁷Li NMR, static ⁷Li and ¹H NMR, and spin‐lattice T₁(⁷Li)/T₁(¹H) relaxation experiments. It is determined that only Li⁺ contributes to long‐range ion transport, while H⁺ dynamics is constrained to an incomplete isotropic rotation of the OH group. The results uncover detailed mechanistic understanding of the ion transport in Li₂OHCl. It is shown that two distinct phases of ionic motions appear at low and elevated temperatures, and that the rotation of the OH group controls Li⁺ and H⁺ dynamics in both phases. The model based on the NMR experiments is fully consistent with crystallographic information, ionic conductivity measurements, and Born–Oppenheimer molecular dynamic simulations.     

Lithium–Iron (III) Fluoride Battery with Double Surface Protection

Lithium–metal fluoride batteries promise significantly higher energy density than the state‐of‐the‐art lithium‐ion batteries and lithium–sulfur batteries. Unfortunately, commercialization of metal fluoride cathodes is prevented by their high resistance, irreversible structural change, and rapid degradation. In this study, a substantial boost in metal fluoride (MF) cathode stability by designing nanostructure with two layers of protective shells—one deposited ex situ and the other in situ is demonstrated. Such methodology achieves over 90% capacity retention after 300 charge–discharge cycles, producing the first report on FeF₃ as a cathode material, where a very high capacity utilization in combination with excellent stability is approaching the level needed for practical applications of FeF₃. The cathode solid electrolyte interphase (CEI) containing lithium oxalate and B? F bond containing anions is found to effectively protect the cathode material from direct contact with electrolytes, thus greatly suppressing the dissolution of Fe. Quantum chemistry and molecular dynamics calculations provide unique insights into the mechanisms of CEI layer formation. As a result, this work not only demonstrates unprecedented performance, but also provides the reader with a better fundamental understanding of electrochemical behavior of MF cathodes and the positive impact observed with the application of a lithium bis(oxalato)borate salt in the electrolyte.     

Protons Enhance Conductivities in Lithium Halide Hydroxide/Lithium Oxyhalide Solid Electrolytes by Forming Rotating Hydroxy Groups

Li‐halide hydroxides (Li₂OHX) and Li‐oxyhalides (Li₃OX) have emerged as new classes of low‐cost, lightweight solid state electrolytes (SSE) showing promising Li‐ion conductivities. The similarity in the lattice parameters between them, careless synthesis, and insufficient rigor in characterization often lead to erroneous interpretations of their compositions. Finally, moisture remaining in the synthesis or cell assembling environment and variability in the equivalent circuit models additionally contribute to significant errors in their properties. Thus, there remains a controversy about the real values of Li‐ion conductivities in such SSEs. Here an ultra‐fast synthesis and comprehensive material characterization is utilized to report on the ionic conductivities of contaminant‐free Li2+xOH_1?xCl (x=0‐0.7), and Li₂OHBr not exceeding 10^‐4 S cm^‐1 at 110 °C. Using powerful combination of experimental and numerical approaches, it is demonstrated that the presence of H in these SSEs yields significantly higher Li⁺ ‐ionic conductivity. Born‐Oppenheimer molecular dynamics simulations show excellent agreement with experimental results and reveal an unexpected mechanism for faster Li⁺ transport. It involves rotation of a short OH‐group in SSEs, which opens lower‐energy pathways for the formation of Frenkel defects and highly‐correlated Li⁺ jumps. These findings will reduce the existing confusions and show new avenues for tuning SSE compositions for further improved Li‐ion conductivities.     

Arsenic and Mercury in the Soils of an Industrial City in the Donets Basin,Ukraine

Soil and house dust collected in and around Hg mines and a processing facility in Horlivka, a mid-sized city in the Donets Basin of southeastern Ukraine, have elevated As and Hg levels. Surface soils collected at a former Hg-processing facility had up to 1300 mg kg^?1 As and 8800 mg kg^?1 Hg; 1M HCl extractions showed 74–93% of the total As, and 1–13% of the total Hg to be solubilized, suggesting differential environmental mobility between these elements. In general, lower extractability of As and Hg was seen in soil samples up to 12 km from the Hg-processing facility, and the extractable (1M HCl, synthetic precipitation, deionized water) fractions of As are greater than those for Hg, indicating that Hg is present in a more resistant form than As. The means (standard deviation) of total As and Hg in grab samples collected from playgrounds and public spaces within 12 km of the industrial facility were 64 (±38) mg kg^?1 As and 12 (±9.4) mg kg^?1 Hg; all concentrations are elevated compared to regional soils. The mean concentrations of As and Hg in dust from homes in Horlivka were 5–15 times higher than dust from homes in a control city. Estimates of possible exposure to As and Hg through inadvertent soil ingestion are provided.