Li Metals Research Articles

Tin-based dual-modification enabling enhanced air stability and electrochemical performance for Li5.5PS4.5Cl1.5 in all-solid-state lithium metal batteries

As one of sulfide electrolytes, chlorine-rich lithium argyrodites (Li5.5PS4.5Cl1.5) have significant advantages as solid state electrolytes (SSEs) in all-solid-state batteries (ASSBs) due to their ultra-high conductivity. However, their practical application is limited by poor air stability and weak compatibility with Li metals. Herein, we enhance the performance of Li5.5PS4.5Cl1.5 by doping it with SnO2, resulting in the formation of the Li5.58P0.92Sn0.08S4.34O0.16Cl1.5 electrolyte. The introduction of Sn and O dopants forms strong Sn-S and P-O bonds in the electrolyte, replacing the sensitive P-S bonds and suppressing H2S release. Additionally, this doped electrolyte demonstrates an impressive Li-ion conductivity of 5.71 mS cm−1, a high critical current density of 2.9 mA cm−2, and significantly improved air and moisture stability. Moreover, the Sn dopant produces a Li-Sn alloy layer on the bare Li metal anode, endowing the ASSB with an initial discharge capacity of 146.7mAh/g at 0.2C and a capacity retention of 86.2 % after 200 cycles at 0.5C. Combining with a 10 wt% SnF2-treated Li metal anode to further strengthen the electrode interfacial stability by the in-situ formed Li-Sn and LiF derivatives, the resultant full cell delivers a promoted initial discharge capacity of 179.5mAh/g at 0.2C and a high discharge capacity of 112.2mAh/g after 300 cycles at 0.5C. The dual strategy of electrolyte doping and Li anode modification achieves a synergistic effect that enables the ASSB to exhibit superior electrochemical performance, providing an effective way of preparing stable sulfide-based SSEs for large-scale applications.

Tailoring the grain boundary structure and chemistry of the dendrite-free garnet solid electrolyte Li6.1Ga0.3La3Zr2O12

Garnet-type Li6.1Ga0.3La3Zr2O12 (LGLZO) exhibits high ionic conductivity and extremely low electronic conductivity. The electrochemical properties strongly depend on the characteristics of the grain boundaries and pores in the oxide–ceramic electrolyte. Currently, the main issue of LGLZO is its large grain boundary resistance due to high-temperature sintering. Herein, we propose an effective method for reinforcing the chemical and structural characteristics of the grain boundaries using a Li2O-B2O3-Al2O3 (LBA) sintering aid. In this study, the LBA sintering aid is critical because it fills grain boundaries and void spaces. As a result, LGLZO solid-state electrolytes with sintering aids significantly enhance the ionic conductivity and reduce the activation energy, especially in the grain boundary region. Another crucial issue is the formation of Li dendrites in LGLZO. Since dendritic Li propagates along the grain boundaries, the optimized LGLZO solid-state electrolyte demonstrates excellent stability against Li metals. Overall, the LGLZO electrolyte with the LBA sintering aid exhibits stable long-term cycling performance due to the well-designed grain boundaries.

An effective tandem leaching method for recovering precious metals from depleted ternary lithium-ion batteries

The increasing volume of spent ternary lithium batteries necessitates the development of an environmentally friendly and efficient recycling process tailored for these batteries. This paper introduces an innovative leaching system that employs oxalic acid and its derivative, Deep Eutectic Solvents (DES), as leaching agents, specifically designed to selectively recover Li and other valuable metals from the cathode materials of discarded ternary lithium batteries, Li(NixCoyMn1-x-y)O2 (NCM). These findings indicate that oxalic acid is capable of selectively leaching Li without the need for reducing agents, whereas DES effectively segregates and leaches other valuable metals. The optimal parameters determined through orthogonal experiments for the initial leaching stage included a solid-to-liquid ratio of 15 g L−1, leaching duration of 3 h, temperature of 75 °C, and stirring speed of 400 rpm, resulting in a Li leaching rate of 99.95%. In the subsequent step, DES enabled the precipitation of Ni and the leaching of Co and Mn within 2 h at 110 °C, achieving recovery rate of 99.88% for Ni, 98.1% for Co, and 90% for Mn, while also significantly optimizing the recovery conditions. This breakthrough may offer an environmentally benign and effective method for the selective recovery of Li and other valuable metals.

Facile Polymer of Intrinsic Microporosity-Modified Separator with Quite-Low Loading for Enhanced-Performance Lithium Metal Batteries.

Lithium metal batteries (LMBs) using Li metals as anodes are conspicuous for high-energy-density energy-storage devices. However, the nonuniform deposition of Li+ ions leading to uncontrolled Li dendrite growth, which adversely affects electrochemical performance and safety, has impeded the practical application of lithium metal batteries (LMBs). Herein, PIM-1, a type of polymer of intrinsic microporosity (PIM), was utilized for surface engineering of conventional polyolefin separators. This process resulted in the formation of a continuous and homogeneous coating across the separator, facilitating uniform Li+ ion flux and deposition, and consequently reducing dendrite formation. Notably, the loading mass was quite low (0.6 g/m2) through the convenient dipping method. The intrinsic micropores and polar groups (cyano and ether groups) of PIM-1 greatly improved the electrolyte wettability and ionic conductivity of commercial polypropylene (PP) separators. And the PIM-1 coating guided Li+ flux to achieve uniform Li deposition. Moreover, the polar groups (cyano and ether groups) of PIM-1 are beneficial to the desolvation of Li+-solvates. As a result, the synergetic effect of uniform Li+ flux, desolvation, and enhanced mechanical strength of separators brings about considerable improvement in cycle life, suppression of Li dendrite, and Coulombic efficiency for LMBs. As this surface engineering is simple, relatively low-cost, and effective, this work provides fresh insights into separators for LMBs.

A theoretical study on the electronic and optical properties of M-TiO2/ZnO (M=Li, Na, K, Fe) toward application in photocatalysis

This study employs the tight-binding density functional method GFN1-xTB to investigate the structural and electronic properties of TiO2-ZnO and TiO2-ZnO composite materials modified by Li, Na, K, and Fe metals. Computational analyses reveal the formation of weak covalent bonds between the TiO2 and ZnO components within the composite system. Doping TiO2-ZnO with metals induces significant alterations in the electronic structure, particularly in terms of ionization energy and global electrophilic index. The UV-VIS spectra are calculated using real-time time-dependent density functional theory with xTB Hamiltonians. The obtained results demonstrate minimal impact of metal presence on the absorption spectrum of TiO2-ZnO, but significant influence on the recombination potential of photogenerated charge carriers. It is suggested that Fe/TiO2-ZnO and Li/TiO2-ZnO will demonstrate higher photocatalytic activity than the pristine TiO2-ZnO material.

Heavy metals toxicity on epigenetic modifications in the pathogenesis of Alzheimer's disease (AD).

Alzheimer's disease (AD) is a progressive decline in cognitive ability and behavior which eventually disrupts daily activities. AD has no cure and the progression rate varies unlikely. Among various causative factors, heavy metals are reported to be a significant hazard in AD pathogenesis. Metal-induced neurodegeneration has been focused globally with thorough research to unravel the mechanistic insights in AD. Recently, heavy metals suggested to play an important role in epigenetic alterations which might provide evidential results on AD pathology. Epigenetic modifications are known to play towards novel therapeutic approaches in treating AD. Though many studies focus on epigenetics and heavy metal implications in AD, there is a lack of research on heavy metal influence on epigenetic toxicity in neurological disorders. The current review aims to elucidate the plausible role of cadmium (Cd), iron (Fe), arsenic (As), copper (Cu), and lithium (Li) metals on epigenetic factors and the increase in amyloid beta and tau phosphorylation in AD. Also, the review discusses the common methods of heavy metal detection to implicate in AD pathogenesis. Hence, from this review, we can extend the need for future research on identifying the mechanistic behavior of heavy metals on epigenetic toxicity and to develop diagnostic and therapeutic markers in AD.

A tandem approach for precipitant-free highly selective recovery of valuable metals from end-of-life lithium-ion batteries using a green deep eutectic solvent

Recently, recycling lithium-ion batteries (LIBs) waste and the efficient recovery of valuable metals has become crucial for the circular economy. Deep eutectic solvents (DESs) have shown immense potential for metal extraction from end-of-life (EoL) LIBs. However, a complicated subsequent separation process is required due to the non-selectivity of the DES components for metal. Herein, we propose a tandem precipitant-free hydrometallurgical process for the selective recovery of Li and other valuable metals (Ni, Co, Mn) from EoL LIBs using a green DES. The process parameters, viz., reaction temperature (T), time (t), pulp density (S/L), and molar ratio (MR) of ethylene glycol to tartaric acid, were optimized via the statistical optimization technique of response surface methodology. The results revealed maximum extraction efficiencies of 99.2 ± 0.5%, 96.1 ± 1.4%, 95.2 ± 1.2%, and 97.8 ± 1.5% for Li, Ni, Co, and Mn, respectively, under the optimized process conditions of T = 118 °C, t = 17 min, S/L = 42 g/L, and MR = 3:1. The kinetic study showed that interfacial reaction governed the extraction process. A plausible mechanism depicting the role of DES constituents in synergistically facilitating the extraction reaction was elucidated. Moreover, Li and other metals (Ni, Co, and Mn) were selectively separated and recovered with an overall efficiency of ∼99%. The reusability of the recovered metal products and the DES were also assessed for a closed-loop recycling process. At the outset, the proposed process paves the way for a greener alternative for recycling valuable metals from EoL LIBs rather than conventional acid-based leaching processes.

Intelligent Stress‐Adaptive Binder Enabled by Shear‐Thickening Property for Silicon Electrodes of Lithium‐Ion Batteries

AbstractElastic binders with supramolecular interactions are widely explored to mitigate the stress caused by the volume expansion of electrode materials, such as Si, S, or Li metals, in next‐generation secondary batteries. Herein, a new class of elastic binders is proposed with an automatic stress‐control mechanism capable of responding in real time to dynamic local stress variations. Specifically, this study focuses on the shear‐thickening behavior, wherein polymers automatically amplify their viscoelasticity in response to local shear‐stress changes. To realize an intelligent stress‐adaptive binder, starch analogs exhibiting shear‐thickening properties and unique crystallinity are employed as binders for highly expandable Si anodes. The shear‐thickening mechanism is comprehensively investigated using deep‐learning‐based molecular dynamics (MD) simulations and in situ transmission electron microscopy (TEM) analysis, which determines the optimal conditions for effectively limiting dynamic local surface expansion. Among the starch analogs, the amylose and long‐chain amylopectin (AMLAP) binder demonstrates improved high‐rate capability (1710 mAh g−1 at 5 C) and superior reversible capacity (2025 and 1493 mAh g−1 after 100 and 500 cycles, respectively, at 1 C) with optimal shear‐thickening properties. Furthermore, AMLAP exhibits favorable characteristics for affordable large‐scale production. Hence, this study clearly demonstrates that the shear‐thickening properties of binders can be considered a new factor in fabricating stable electrodes with extremely expandable materials.

Designing Low Toxic Deep Eutectic Solvents for the Green Recycle of Lithium-Ion Batteries Cathodes.

The Lithium-ion battery (LIB) is one of the main energy storage equipment. Its cathode material contains Li, Co, and other valuable metals. Therefore, recycling spent LIBs can reduce environmental pollution and resource waste, which is significant for sustainable development. However, traditional metallurgical methods are not environmentally friendly, with high cost and environmental toxicity. Recently, the concept of green chemistry gives rise to environmental and efficient recycling technology, which promotes the transition of recycling solvents from organic solvents to green solvents represented by deep eutectic solvents (DESs). DESs are considered as ideal alternative solvents in extraction processes, attracting great attention due to their low cost, low toxicity, good biodegradability, and high extraction capacity. It is very important to develop the DESs system for LIBs recycling for sustainable development of energy and green economic development of recycling technology. In this work, the applications and research progress of DESs in LIBs recovery are reviewed, and the physicochemical properties such as viscosity, toxicity and regulatory properties are summarized and discussed. In particular, the toxicity data of DESs are collected and analyzed. Finally, the guidance and prospects for future research are put forward, aiming to explore more suitable DESs for recycling valuable metals in batteries.

Solution to the schrödinger equation for bound states of polar molecules using shallow neural networks

The time independent Schrödinger equation can be solved analytically in very few cases. This is why scientists rely on approximate numerical methods. One that is yet to be a part of the everyday toolbox for physicists are neural networks. With it, it is possible to calculate eigenfunctions and the energy spectra of bound states. A double exponential central potential is used to describe the interaction between two electric dipoles that form through van der Waals interactions. These systems can be important when the electric dipoles are very large and differ from covalent, ionic, and other kinds of bonds, as is the case of the monomers M−C60, where M=Cs,Li or other alkali metals. Based in statistical physics, it has been shown that a dimer can be formed through a spontaneous and exothermic reaction. The ground state and the first two excited states of this system were calculated, also the solutions and their associated energies were plotted. The result for the ground state is compared to the shooting method and the direct variational method. The numerical value of the ground states obtained suggests that the dimers can be dissociated by electromagnetic waves with wavelengths in the far infrared regime, very close to microwaves.

Co-synthesis and Electrochemical Investigation of the Nitrogen-Doped Carbon Layer with Metallic Nano Beads on the SiOx Anode for Lithium Secondary Batteries.

The high theoretical capacity (∼2000 mAh g-1) of silicon suboxide (SiOx, with 1 < x < 2) can solve the energy density issue of the graphite anode in Li-ion batteries. In addition, it has an advantage in terms of volume expansion or side reactions compared to pure Si or Li metals, which are considered as next-generation anode materials. However, the loading content of SiOx is limited in commercial anodes because of its low cycle stability and initial coulombic efficiency. In this study, a nitrogen-doped carbon layer with Cu beads (N-C/Cu) derived from copper phthalocyanine (CuPc) is applied to a SiOx electrode to improve its electrochemical performance. The SiOx electrode is simultaneously coated with a Cu- and N-doped carbon layer using CuPc. N-C/Cu synergistically enhances the electric conductivity of the electrode, thus improving its electrochemical performance. The SiOx/N-C/Cu composite has better cyclability and higher capacity (1095.5 mAh g-1) than the uncoated electrode, even after 200 cycles in the 0.5 C condition. In full-cell cycling with NCM811 cathodes, the SiOx (60 wt % of SiOx, with a n/p ratio of 1.1) and graphite-mixed (7.8 wt % of SiOx, with a n/p ratio of 1.1) anodes also show improved electrochemical performances in the same conditions.

Enhanced lithium dendrite suppression ability through SiO2 substitution in superionic halogen-rich argyrodites and their application in all-solid-state lithium batteries

Among the inorganic solid electrolytes, it has been reported that argyrodites of sulfide-based electrolyte systems have a number of advantages, including high ionic conductivity and mechanical flexibility. Despite these advantages, their poor compatibility with Li metal still represents a problem. In this work, we prepared a halogen-rich argyrodites Li6-xPS5-xCl1+x solid electrolyte using a high-energy ball milling process. According to the composition test, Li5.3PS4.3Cl1.7 exhibited a high ionic conductivity (9.0 mS cm−1) at room temperature. Thus, we proposed SiO2 doped halogen-rich argyrodites while aiming to achieve improved electrochemical performance and the ionic conductivity. At a value of 9.4 mS cm−1, the ionic conductivity of Li5.34P0.96Si0.04S4.22O0.08Cl1.7 compositions was slightly increased compared to that of Li5.3PS4.3Cl1.7 (9.0 mS cm−1). Moreover, that composition showed a higher critical current density (1.0 mA cm−2) than that of Li5.3PS4.3Cl1.7 (0.35 mA cm−2), indicating that SiO2 doped Li5.3PS4.3Cl1.7 solid electrolyte improved the compatibility of the electrolyte against Li metal by reducing the side reaction with the Li metals. The air stability was also enhanced after SiO2 doping. These results confirmed that metal oxide doping in halogen-rich argyrodites contributed to high ionic conductivity and good electrochemical performance.

An electrolysis–displacement–distillation approach for the production of Li, Mg, Ca, Sr, and Ba metals

This paper describes a new advancement in the field of green energetic metal production, a finding that unlocks access to extracting Li, Mg, Ca, Sr, and Ba metals that are hitherto produced with the generation of Cl2 and heavy CO2.

Superior electrochemical performance of alkali metal anodes enabled by milder Lewis acidity

Weak Lewis acidity of potassium-ions promotes enhanced anion incorporation into the solvation shell, facilitating the formation of a more stable and dissolution-resistant solid electrolyte interphase for K metal compared with that for Li and Na metals.

Amorphous Li2O–LiI–MoO3 solid electrolytes: mechanochemical synthesis and application to all-solid-state batteries

Amorphous-type Li2O–LiI–MoO3 solid electrolytes prepared using a mechanochemical method exhibit a high ionic conductivity of 10−5 S cm−1 at 25 °C, sufficient ductility to densify by pressing at room temperature, and stability to Li metals.

Role of Copper as Current Collectors in the Reductive Reactivity of Polymers for Anode-Free Lithium Metal Batteries - Insights from DFT and AIMD Studies

Understanding the role of current collectors (CCs) in the reductive reactivity of polymers on Li metal and the resultant solid electrolyte interphase (SEI) formation is essential for improving the performance of anode-free lithium metal batteries (AFLMBs). In this study, we have examined the reactivity of three polymeric hosts: poly(ethylene oxide) (PEO), poly(ε-caprolactone) (PCL), and poly(trimethylene carbonate) (PTMC) at Li metal supported on Cu surfaces (Li/Cu) using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. In particular, the effect of copper (Cu) CCs on polymer stability, electronic structure, and their reduction reactions is investigated and compared to that of pure Li (100) surface. Through time-dependent Bader charge transfer analysis, electron transfer is identified as the triggering factor for polymer reduction. Based on the simulations, we find that the Cu CCs have a significant influence on the charge distribution of the Li metals, which increases electron transfer to the polymers and thereby accelerates polymers reduction. This thereby leads to different reaction mechanisms as compared to on Li-metal. The findings suggest that utilization of Cu CCs avoid production of CO molecules and improves the quality of the formed SEI layer. Figure 1

Interface Induced Fast Ion Conduction in Complex Hydride/Oxide Nanocomposites: Interplay between Hydride and Oxide Properties

Solid-state electrolytes are crucial for next generation batteries with high energy density, long lasting and improved safety. The compatibility of most solid electrolytes with metallic anodes such as Li and Na metals, and cathodes such as sulfur, makes them suitable for high-capacity batteries (e.g., Li-S). They also address the safety concerns of current batteries by eliminating the flammable organic solvents in liquid electrolytes and by preventing/limiting dendrite formation. The lithium and sodium containing complex metal hydrides (e.g., LiBH4, NaBH4, LiCB11H12) have recently gained attention as solid-state electrolyte. They show high ionic conductivities but only at elevated temperatures (typically above 110 °C). Extending the high ionic conductivities to ambient temperatures is pivotal to the application of this fascinating class of solid electrolytes [1]. In this contribution, we will use LiBH4 and NaBH4 as examples to show that the ionic conductivities of complex hydrides can be greatly enhanced through interface effects resulting from the formation of nanocomposites with metal oxides. This strategy can lead to several orders of magnitude increase in the room temperature ionic conductivity [2]. Using DSC, DRIFT, solid-state NMR, and XRS (Xray Raman scattering), I will discuss how nanocomposite formation and presence of interfaces modifies either the phase stability, the defect concentration and/or leads to the formation of tertiary phase, and thereby increase profoundly the ion mobility of the complex hydrides. Systematic studies with different oxide nanoscaffolds and surface modified metal oxides, reveal that these effects can be optimized by tuning/engineering the nanostructure and interfaces in the nanocomposites. [3-4]. We will show that the effects also depend on a complex interplay between the stability of the metal hydride and surface properties of the metal oxide. Finally, the performance of some of the nanocomposite electrolytes in all-solid-state batteries, will be highlighted [5] References [1] L.M de Kort, P. Ngene et al. J. Journal of Alloys and Compounds 901 (2022) 163474[2] D. Blanchard et al., Advanced Functional Material. 25 (2015), 182.[3] P. Ngene et al. Physical Chemistry Chemical Physics 21 (40), 22456-22466[4] L.M de Kort, P. Ngene et al. Journal of Materials Chemistry A 8.39 (2020): 20687-20697[5] D. Blanchard et al, J. Electrochem. Soc. (2016).

Role of copper as current collectors in the reductive reactivity of polymers for anode-free lithium metal batteries - Insights from DFT and AIMD studies

Understanding the role of current collectors (CCs) in the reductive reactivity of polymers on Li metal and the resultant solid electrolyte interphase (SEI) formation is essential for improving the performance of anode-free lithium metal batteries (AFLMBs). In this study, we have examined the reactivity of three polymeric hosts: poly(ethylene oxide) (PEO), poly(ε-caprolactone) (PCL), and poly(trimethylene carbonate) (PTMC) at Li metal supported on Cu surfaces (Li/Cu) using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. In particular, the effect of copper (Cu) CCs on polymer stability, electronic structure, and their reduction reactions is investigated and compared to that of pure Li (100) surface. Through time-dependent Bader charge transfer analysis, electron transfer is identified as the triggering factor for polymer reduction. Based on the simulations, we find that the Cu CCs have a significant influence on the charge distribution of the Li metals, which increases electron transfer to the polymers and thereby accelerates polymers reduction. This thereby leads to different reaction mechanisms as compared to on Li-metal. The findings suggest that utilization of Cu CCs avoids the production of CO molecules and improves the quality of the formed SEI layer.

Evaluation of heavy metal contamination using cokriging geostatistical method (case study of Abteymour oilfield in southern Iran)

One of the most significant sources of soil contamination is the industries involved in the discovery, extraction, and use of petroleum and gas resources. One of the largest oil fields in Iran is the Abteymour oilfield, which is situated in the agricultural areas and Karun river flood plain. This study was carried out to analyze and monitor soil contamination by heavy metals and to create a map of the spread of contamination in the vicinity of the Abteymour oilfield, taking into account the significance of soil pollution in such a region. Thirty-three samples from the local surface soils were used in this study, and in addition to testing the ICP-MASS device's ability to detect the presence of heavy metals and other key elements, some of the soil's physical and chemical characteristics were also determined. After drawing the variograms and determining the appropriate fitting model, the cokriging method was used to study the spatial distribution of Al, Ti, Sr, Cr, Ni, V, Cu, Li, and Pb heavy metals and Na and S elements. The results of the heavy metals distribution in the studied area showed that the distribution of the studied elements is affected by geological conditions and human activities, including the petroleum industry and agriculture activities.

Mechanistic Study of Lithium Electrodeposition Using Dynamic Electrochemical Impedance Spectroscopy

Lithium metal batteries have increased energy density over standard graphite-based Li-ion anodes. However, Li metal anodes have difficulty forming stable passivation layer (called solid electrolyte interphase, SEI) leading to poor use of Li inventory. That is, LI metals require larger cathode loading, which reduces the energy density gain. A holistic approach to Li anode incorporation includes electrolyte design, mechanism understanding, and battery engineering. A factor that has not been fully appreciated is the nature of the Lithium metal itself, namely its SEI before incorporation into the battery device may affect the subsequent SEI formation. Here, we present a mechanistic study on lithium SEI formation on various lithium sources, as well as the Li cycling.We utilized dynamic impedance spectroscopy (dEIS) to probe the formation and evolution of the SEI during Li cycling of various Li sources. dEIS superimposes a multisine waveform atop the dc stimulus signal. After applying a sliding window FFT protocol that takes the complex ratio of the measured potential and current signals time-resolved complex impedance can be obtained. We will discuss the differences between the Li cycling profiles using Lipon (a glassy solid electrolyte) and a liquid electrolyte. We will relate the differences in cycling performance, particularly the SEI evolution to the surface chemistry of the as-received Li metal source.The US Department of Energy's Energy Efficiency and Renewable Energy Vehicles Technologies Office provided funding for this work under the US-German Cooperation on Energy Storage: Lithium-Solid-Electrolyte Interfaces program.