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At least 235 records · Page 13

Development of an interatomic potential for the Ta–Li system

A new interatomic potential for the Ta–Li system is introduced to facilitate the study of phase stability, mechanical properties and non-equilibrium dynamics after Li implantation in Ta. Here, this potential is based on a generalization of the embedded atom method (GEAM) and includes contributions from embedding energy, explicit two- and three-body interactions, and nonlocal many-body interaction terms. The parameters of the potential are optimized using energies and atomic forces for a wide range of configurations obtained from ab initio density functional theory (DFT) calculations. The potential is rigorously validated across a range of physical properties, including elastic constants, equations of state, phonon dispersion curves, point defect properties, and melting temperatures for different compositions. Although our potential is trained on a small dataset, its accuracy is comparable to that of available machine learning potentials for Li and Ta. Our simulations show that at temperatures below 500 K, Li atoms in Ta–Li alloys form clusters separated by Ta-rich domains, and we find no evidence of ordered phase formation. For Li concentrations below a few percent, Li atoms preferentially segregate to surfaces and grain boundaries. However, in alloys containing more than ~10% Li, the accumulation of Li in symmetric-tilt grain boundaries can lead to one of the following effects: formation of amorphous-like regions, changes in grain boundary structural units, or lateral movement of the grain boundary.

GEAM potential↗

Improved cycle stability and high-rate capability of LiNbO 3 -coated Li 3 VO 4 as anode material for lithium-ion battery

Lithium vanadate (Li 3 VO 4 ) has garnered considerable attention as an alternative negative electrode material for non-aqueous lithium-ion batteries due to its high capacity, energy efficiency, and stable discharge voltage. Nonetheless, the Li 3 VO 4 material displays a low rate capability, attributed mainly to its poor intrinsic electronic conductivity. Here, in this study, we report the synthesis of lithium niobate LiNbO 3 -coated Li 3 VO 4 (LVO@LNO) using a one-pot sol-gel method. The resulting LVO@LNO demonstrates a high reversible capacity of approximately 530 mAh/g, which is more than double that of free Li 3 VO 4 . To explore the effect of the LNO coating process on the morphological and structural properties, Raman, XRD, operando XRD, XPS, SEM and HTEM analyses were conducted. To explain the enhancement of electronic conductivity in our modified material after a LiNbO 3 coating, we conducted an Ex-Situ electrochemical impedance (EIS) and Density Functional Theory (DFT) computational study. Additionally, we designed a full cell utilizing a 1 wt% LNO-coated LVO anode and NMC-811 cathode. The cell yielded an output voltage of approximately 2.8 V with a high initial specific capacity of 350 mAh/g versus to the anode, at 1C with a capacity retention of 85 % after 100 cycles.

25 ENERGY STORAGE↗

Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries

Electrolyte engineering is critical for developing Li metal batteries. While recent works improved Li metal cyclability, a methodology for rational electrolyte design remains lacking. In this study, we propose a design strategy for electrolytes that enable anode-free Li metal batteries with single-solvent single-salt formations at standard concentrations. Rational incorporation of –CF 2 – units yields fluorinated 1,4-dimethoxylbutane as the electrolyte solvent. Paired with 1 M lithium bis(fluorosulfonyl)imide, this electrolyte possesses unique Li–F binding and high anion/solvent ratio in the solvation sheath, leading to excellent compatibility with both Li metal anodes (Coulombic efficiency ~ 99.52% and fast activation within five cycles) and high-voltage cathodes (~6 V stability). Fifty-μm-thick Li|NMC batteries retain 90% capacity after 420 cycles with an average Coulombic efficiency of 99.98%. Industrial anode-free pouch cells achieve ~325 Wh kg –1 single-cell energy density and 80% capacity retention after 100 cycles. Our design concept for electrolytes provides a promising path to high-energy, long-cycling Li metal batteries.

25 ENERGY STORAGE↗

Theoretical Design of Lithium Chloride Superionic Conductors for All-Solid-State High-Voltage Lithium-Ion Batteries

The development of solid electrolytes (SEs) is a promising pathway to improve the energy density and safety of conventional Li ion batteries. Several lithium chloride SEs, Li 3 MCl 6 (M = Y, Er, In, and Sc), have gained popularity due to their high ionic conductivity, wide electrochemical window, and good chemical stability. This study systematically investigated 17 Li 3 MCl 6 SEs to identify novel and promising lithium chloride SEs. Calculation results revealed that 12 Li 3 MCl 6 (M = Bi, Dy, Er, Ho, In, Lu, Sc, Sm, Tb, TI, Tm, and Y) were stable phase with a wide electrochemical stability window and excellent chemical stability against cathode materials and moisture. Li-ion transport properties were examined using bond valence site energy (BVSE) and ab initio molecular dynamics (AIMD) calculation. Li 3 MCl 6 showed the lower migration energy barrier in monoclinic structures, while orthorhombic and trigonal structures exhibited higher energy barriers due to the sluggish diffusion along the two-dimensional path based on the BVSE model. AIMD results confirmed the slower ion migration along the 2D path, exhibiting lower ionic diffusivity and higher activation energy in orthorhombic and trigonal structures. For the further increase of ionic conductivity in monoclinic structures, Li-ion vacancy was formed by the substitution of M 3+ with Zr 4+ . Zr-substituted phase (Li 2.5 M 0.5 Zr 0.5 Cl 6 , M = In, Sc) exhibited up to a fourfold increase in ionic conductivity. This finding suggested that the optimization of Li vacancy in the Li 3 MCl 6 SEs could lead to superionic Li 3 MCl 6 SEs.

25 ENERGY STORAGE↗

Precious metal oxygen-evolving anodes for electrolytic reduction of metal oxides in molten LiCl-Li 2 O electrolyte

Understanding the electrochemical stability of oxygen-evolving anode materials in molten salt electrolytes is essential to enable decarbonized electrolytic reduction of metal oxides (e.g., used nuclear oxide fuels). Here, this work investigated three precious metals (Ir, Ru, and Pt) as oxygen-evolving anodes in molten LiCl-Li 2 O (99.0-1.0 wt%) at 650 °C. For consistent measurements, this work employed a three-electrode cell comprised of a two-phase Li-Bi (65-35 at%) reference electrode and a NiO counter electrode. Anodic polarization behavior of each anode was investigated via cyclic voltammetry (CV) and chronoamperometry. The onset potential for oxygen evolution was observed at E > 2.9 V (vs. Li/Li + ) for the Ir and Ru anodes and anodic current density was as high as 1.0 A cm -2 at 3.23 V. The dimensional stability of each anode was evaluated from long-term electrolysis experiments (10.0-32.1 h) at 3.23 V. Rapid consumption of the Pt anode was observed after the application of 26,453 C cm -2 with a reduction in diameter of about 15.8% due to the formation of a non-protective Li 2 PtO 3 compound. The formation of this compound was also observed during CV measurements as additional anodic waves at potentials more negative than that of oxygen evolution. In contrast, both the Ir and Ru anodes exhibited excellent dimensional stability with a reduction in diameter or thickness of less than 1.5% even after applying greater charge density of ~41,100 C cm -2 , demonstrating superior stability during oxygen evolution in the LiCl-Li 2 O electrolyte.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Manganese‐Based Spinel Cathodes: A Promising Frontier for Solid‐State Lithium‐Ion Batteries

Recently, all-solid-state lithium-ion batteries (ASSLIBs), which exhibit improved safety and enhanced energy density compared to conventional commercialized lithium-ion batteries (LIBs), thereby have garnered extensive research interest. Among the promising cathode candidates, Mn-based spinel cathodes LiMn 2 O 4 (LMO) and LiNi 0.5 Mn 1.5 O 4 (LNMO), with the unique characteristics of low cost, structural stability, and 3D Li-ion diffusion channels, have demonstrated excellent performance in LIBs and presented great potential in ASSLIBs applications. However, several challenges, including structural degradations, poor interfacial contact, large interfacial resistance, and Mn-dissolution/diffusion during the electrochemical cycling, hinder their practical applications and commercialization in the ASSLIBs. Particularly, the high-voltage LNMO cathodes suffer from the challenge of electrochemical incompatibility with most of the solid-state electrolytes (SSEs). Herein, the spinel structure, the electrochemical behavior, and the structural degradation of the LMO/LNMO are explored. The characteristics and recent progress of the mitigating strategies to the challenges of various SSEs, including polymer-, oxide-, composite-, sulfide-, halide-, and LiPON-based SSEs, are introduced when paired with LMO/LNMO. Finally, the directions for future research to advance Mn-based spinel cathodes and fulfill the requirements of the next-generation ASSLIBs are also discussed.

Dou, Yu [Concordia University, Montreal, QC (Canad↗

A Coordinated-Anion-Enriched Electrolyte for Lean-Electrolyte Li–S Batteries

The solid electrolyte interphase (SEI) on Li and cathode electrolyte interphase (CEI) at sulfurized polyacrylonitrile (SPAN) formed in the commonly used liquid electrolytes cannot accommodate the large volume change of both Li anode and SPAN cathode, resulting in severe electrolyte and Li consumption and fast capacity decay under high mass loading and lean electrolyte condition. Herein, a LiF-rich SEI and a LiF-Li x N y O z co-enriched CEI are simultaneously formed by adding ionic liquid (Py 13 TFSI) in the localized high-concentration electrolyte (LHCE), which forms a coordinated-anion-enriched solvation structure. In this study, the LiF-rich interphase results in less stress/strain during large volume changes of Li and SPAN and therefore achieving obviously improved stability even at a high areal capacity. Consequently, Li (50 μm)||SPAN (6 mg cm -2 ) pouch cells under the lean electrolyte condition (E/S ratio of 5 mL g SPAN -1 ) delivers a stable cycle life of 120 cycles with 79.2% capacity retention, demonstrating great promise for high-energy-density lithium-sulfur batteries.

25 ENERGY STORAGE↗

Computational study of Li3BO3 and Li3BN2 I: Electrolyte properties of pure and doped crystals

Both Li3BO3 and Li3BN2 materials have promising properties for use in all-solid-state batteries and other technologies dependent on electrolytes with significant ionic conductivity. As the first of a two-part study, this paper reports the analysis of detailed simulations of Li ion diffusion in the monoclinic forms of these materials. Using both NEB and MD methods, it is clear that Li ion migration via vacancy mechanisms provides the most efficient ion transport in each material. While the results suggest that interstitial defects in these materials do not play a direct role in Li ion migration, their relative stability seems to enhance vacancy production via the formation of Frenkel-type defects. This may partially explain why the Li ion conductivities computed from MD simulations of samples initially containing a single Li ion vacancy are in reasonable agreement with measured values of this work for Li3BO3 and those reported in the literature for poorly crystalline samples of both materials. The possibility of increasing vacancy concentrations by substitutional doping (F for O in Li3BO3 and C for B in Li3BN2) is also examined, finding simulated conductivities comparable to those of the ideal vacancy model.

Li, Yan↗

Study on the Thermal Stabilizing Process of Layered Double Hydroxides in PVC Resin

Poly(vinyl chloride) (PVC) is widely used in various fields and requires the use of thermal stabilizers to enhance its thermal stability during processing because of its poor thermal stability. Layered double hydroxides (LDHs) are widely considered to be one kind of highly efficient and environmentally friendly PVC thermal stabilizer. To investigate the thermal stabilizing process of layered double hydroxides (LDHs) in PVC resin, PVC and MgAl-LDHs powders with different interlayer anions (CO 3 2- , Cl - , and NO 3 - ) were physically mixed and aged at 180 °C. The structure of LDHs at different aging times was studied using XRD, SEM, and FT-IR. The results show that the thermal stabilizing process of LDHs on PVC mainly has three stages. In the first stage, the layers of LDHs undergo a reaction with HCl, which is released during the thermal decomposition of PVC. Subsequently, the ion exchange process occurs between Cl - and interlayer CO 3 2- , resulting in the formation of MgAl-Cl-LDHs. Finally, the layers of MgAl-Cl-LDHs react with HCl slowly. During the thermal stabilizing process of MgAl-Cl-LDHs, the peak intensity of XRD reduces slightly, and no new XRD peak emerges. It indicates that only the first step happens for MgAl-Cl-LDHs. The TG-DTA analysis of LDHs indicates that the interaction of LDHs with different interlayer anions has the following order: NO 3 - < CO 3 2- < Cl - , according to the early coloring in the thermal aging test of PVC composites. The results of the thermal aging tests suggest that LDHs with a weak interaction between interlayer anions and layers can enhance the early stability of PVC significantly. Furthermore, the thermal aging test demonstrates that LDHs with high HCl absorption capacities exhibit superior long-term stabilizing effects on PVC resin. This finding provides a valuable hint for designing an LDHs/PVC resin with a novel structure and excellent thermal stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Boosting the cycling stability of Ni-rich layered oxide cathode by dry coating of ultrastable Li 3 V 2 (PO 4 ) 3 nanoparticles

Nickel (Ni)-rich layered oxides such as LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) represent one of the most promising candidates for next-generation high-energy lithium-ion batteries (LIBs). However, the pristine Ni-rich cathode materials usually suffer from poor structural stability during cycling. In this work, we demonstrate a simple but effective approach to improve the cycling stability of the NCM622 cathode by dry coating of ultrastable Li 3 V 2 (PO 4 ) 3 -carbon (LVP-C) nanoparticles, which leads to a robust composite cathode (NCM622/LVP-C) without sacrificing the specific energy density compared with pristine NCM622. The optimal NCM622/LVP-C composite presents a high specific capacity of 162 mA h g -1 at 0.5 C and excellent cycling performance with 85.0% capacity retention after 200 cycles at 2 C, higher than that of the pristine NCM622 (67.6%). Systematic characterization confirms that the LVP-C protective layer can effectively reduce the side reactions, restrict the cation mixing of NCM622 and improve its structural stability. Moreover, the NCM622/LVP-C||graphite full cells also show a commercial-level capacity of 3.2 mA h cm -2 and much improved cycling stability compared with NCM622/LVP-C||graphite full cells, indicating the great promise for low-cost, high-capacity and long-life LIBs.

36 MATERIALS SCIENCE↗

Irreversible Multielement Diffusion and the Resulting Compositional and Processing Flexibility in the Synthesis and Densification of Lithium Aluminum Lanthanum Zirconium Oxide

Despite the broad interest in Al-doped lithium lanthanum zirconium oxide (LLZO), the wide range of reported ionic conductivities suggests that the effect of processing parameters on the resulting phase purity and bulk conductivity is not well-understood. Here, in this work, we synthesized six separate series of LLZO with variations in Al concentration, Li excess, Li addition order, Li source, densification method, and mother powder to determine the effect on the composition, phase purity, density, and bulk conductivity. We found that a wider range of compositions (6.08–7.61 mol of Li and 0.06–0.23 mol of Al) than previously reported can result in cubic phase stability and that nearly all elements (Li, Al, Zr, and La) are lost to the MgO crucible during calcination and sintering. The manner in which different elements are lost is affected by the processing parameters. We observed that Al-doped LLZO shows great compositional flexibility in stabilizing the cubic phase, offering an explanation for the range of electrochemical performance metrics reported in the literature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of the fluorination degree of ether-based electrolyte solvents on Li-metal battery performance

Electrolytes using fluorinated solvents have proven effective in improving the cycling life of Li-metal batteries, by forming a robust solid–electrolyte interphase through decomposition of anion and fluorinated solvent molecules. Herein, we modulated the fluorination degree of ether-based electrolyte solvents to investigate their performance in Li-metal batteries. Here, we tuned the fluorination degree by installing a monofluoro substituent on one ethoxy group of 1,2-diethoxyethane (DEE) and varying the fluorination degree on the other one, providing three fluorinated DEE solvent molecules (i.e., F1F0, F1F1 and F1F2) with a relatively low fluorination degree. All three electrolytes showed improved solvation strength and ionic conductivities compared with previous highly fluorinated DEE electrolytes while retaining good oxidative stability. A full cell test using the Li-metal anode and nickel-rich cathode revealed that a higher degree of fluorination is beneficial to the cycling performance, and the cycling stability follows F1F0 < F1F1 < F1F2. Specifically, F1F0 exhibited poor cycling stability due to its instability against both the anode and cathode. While F1F1 and F1F2 both showed good stability against the Li metal anode, their relative long-term oxidative stability was responsible for the distinct performance, in which the cycle numbers at 80% capacity retention for F1F1 and F1F2 were ~20 and ~80, respectively. Finally, we demonstrated that F1F2 was able to achieve 90 cycles before reaching 80% capacity retention in practical lithium iron phosphate (LFP) pouch cells. This work shows the importance of modulating the fluorination degree of electrolyte solvents, and this approach is suitable for various cathode materials.

25 ENERGY STORAGE↗

Recent progress and future prospects of atomic layer deposition to prepare/modify solid-state electrolytes and interfaces between electrodes for next-generation lithium batteries

Lithium ion batteries (LIBs) are encouraging electrochemical devices with remarkable properties including a high energy/power density, fast charging capability, and low self-discharge rate. Further increase in energy density as well as safe usage is needed for next-generation LIBs in electric transportation vehicles. Solid-state electrolytes (SSEs) are very promising for high-performance LIBs since they enable improved safety along with increased energy density compared to flammable liquid organic electrolytes. However, utilizing SSEs with a Li metal anode is very challenging due to the possibility of undesired side reactions and the formation of an unstable solid-electrolyte interphase. Therefore, it is critical to enhance the stability of SSEs against the Li anode. One feasible approach is to form a thin and conductive interlayer between the Li anode and solid-state electrolyte. Atomic layer deposition (ALD) is a unique technique for conformal coating of complex 3D structures with finely controlled film thickness (at the atomic scale). ALD coating on the surface of SSEs can be adopted for engineering solid-electrolyte interfaces with desired attributes and improved stability. In this review paper, we have discussed recent progress in implementing the ALD technique for depositing thin layers on various SSE configurations including lithium phosphorus oxynitride (LiPON), garnets, oxides, perovskites, sulphides, Li 3 BO 3 –Li 2 CO 3 (LBCO), and sodium super ionic conductors (NASICON). We have also highlighted the major areas for future research and development in the field. We believe that this review will be very helpful for directing future research on implementing ALD for synthesizing stable and high-performance SSEs with an engineered solid-electrolyte interface for next-generation electrochemical devices (e.g., Li-ion batteries, supercapacitors, and flow batteries).

36 MATERIALS SCIENCE↗

NaSICON-type materials for lithium-ion battery applications: Progress and challenges

Lithium-ion batteries (LIBs) are widely used in electric vehicles, energy storage, smart grids, and portable devices due to their high average output voltage and energy density. NaSICON-type materials have been identified as potential candidates for electrode and solid electrolyte materials for LIBs due to their 3D framework, which contains Li + ions, excellent ionic conductivity, and thermal stability. NaSICON-type materials have a 3D framework and a fast Li + diffusion pathway, making them suitable for use in LIBs. However, their application as solid electrolytes is limited due to poorer ionic conductivity and interfacial stability compared to commercialized liquid electrolytes. Furthermore, their use as electrode materials is restricted by their low electronic conductivity. Here, this review provides an overview of NaSICON-type materials, including their common structure, Li + diffusion mechanism, and preparation strategies. The article also discusses the application and modification strategies of NaSICON-type materials for LIBs, classifying them as anode materials, cathode materials, and solid electrolyte materials. Additionally, the potential use of NaSICON-type materials as modification materials for cathode materials for LIBs is briefly mentioned. Building on previous work on NaSICON-type materials, we propose potential areas for further development and wider applications of these materials in LIBs.

25 ENERGY STORAGE↗

NASICON Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 Solid Electrolyte for an All‐Solid‐State Li‐Metal Battery

Abstract A thin solid electrolyte with a high Li + conductivity is used to separate the metallic lithium anode and the cathode in an all‐solid‐state Li‐metal battery. However, most solid Li‐ion electrolytes have a small electrochemical stability window, large interfacial resistance, and cannot block lithium‐dendrite growth when lithium is plated on charging of the cell. Mg 2+ stabilizes a rhombohedral NASICON‐structured solid electrolyte of the formula Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 (LMZP). This solid electrolyte has Li‐ion conductivity two orders of magnitude higher at 25 °C than that of the triclinic LiZr 2 (PO 4 ) 3 . 7 Li and 6 Li NMR confirm the Li‐ions in two different crystallographic sites of the NASICON framework with 85% of the Li‐ions having a relatively higher mobility than the other 15%. The anode–electrolyte interface is further investigated with symmetric Li/LMZP/Li cell testing, while the cathode–electrolyte interface is explored with an all‐solid‐state Li/LMZP/LiFePO 4 cell. The enhanced performance of these cells enabled by the Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 solid electrolyte is stable upon repeated charge/discharge cycling.

Zhou, Qiongyu↗

Defect-Driven Configurational Entropy in the High-Entropy Oxide Li 1.5 MO 3-δ

Layered lithiated oxides are promising materials for next generation Li-ion battery cathode materials; however, instability during cycling results in poor performance over time compared to the high capacities theoretically possible with these materials. Here, in this paper, we report the characterizations of a Li 1.47 Mn 0.57 Al 0.13 Fe 0.095 Co 0.105 Ni 0.095 O 2.49 high-entropy layered oxide (HELO) with the Li 2 MO 3 structure where M = Mn, Al, Fe, Co, and Ni. Using electron microscopy and X-ray spectroscopy, we identify a homogeneous Li 2 MO 3 structure stabilized by the entropic contribution of oxygen vacancies. This defect-driven entropy would not be attainable in the LiMO 2 structure sometimes observed in similar materials as a secondary phase owing to the presence of fewer O sites and a 3+ oxidation state for the metal site; instead, a Li 2-γ MO 3-δ is produced. Beyond Li 2 MO 3 , this defect-driven entropy approach to stabilizing novel compositions and phases can be applied to a wide array of future cathode materials including spinel and rock salt structures.

25 ENERGY STORAGE↗