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At least 253 records · Page 14

Wet chemical synthesis and properties of argyrodite sulfide solid electrolytes for solid state lithium batteries

The commercialization of the lithium-ion battery (LIB) in 1991 was responsible for the explosion in portable electronic technologies that has been seen over the past 30 years. With the advent of electric vehicles and other high-powered technologies, there is tremendous demand for LIBs with higher energy density and high safety. To achieve this, new electrode materials must be explored. The obvious choice of anode material would be pure metal lithium, which has a theoretical specific capacity of 3860 mAh g-1 . Unfortunately, metal lithium anodes have not been widely commercialized due to their tendency to react violently with the flammable liquid electrolytes used in today’s batteries. Battery safety can best be achieved by adopting solid electrolytes in place of liquid electrolytes. Solid electrolytes are nonvolatile and nonflammable, safely allowing for the combination of high-capacity cathode materials with a Li metal anode. Argyrodite sulfide solid electrolytes such as halogen-doped Li6PS5X (X = Cl, Br, I) are noted for their high ionic conductivity. But before sulfides can be commercially adopted, they possess several disadvantages which must be addressed, including time- and energy-consuming synthesis processes, poor electrochemical stability, and intrinsically poor air stability. This dissertation seeks to address each of these challenges through materials design an synthesis strategies. In this work, we pioneer a solvent-based approach for the synthesis of argyrodite solid electrolytes Li7PS6 and Li6PS5Xinstead of a stringent solid-state synthesis. Nontoxic ethanol is employed as the solvent, enabling a rapid synthetic approach to produce argyrodite solid electrolytes with high phase purity and compositional flexibility. Compared with Li7PS6, halogen doping (i.e. X = F, Cl, Br, I) not only increases the ionic conductivity, but also enhances the electrochemical stability at the interface towards Li metal. Specifically, F-doped argyrodites produce a robust SEI layer containing LiF, contributing to enhanced interfacial stability. Finally, to address the air instability challenge, argyrodite-incorporated composite solid electrolytes (CSEs) are designed and prepared to produce stable and flexible membranes that are demonstrated in solid-state Li metal batteries. These advances push argyrodite sulfide solid electrolyte research further and pave the way for the proliferation of next generation lithium metal batteries.

25 ENERGY STORAGE↗

Tailoring the Reaction Heterogeneity for Robust Li‐Rich Cathodes

The practical application of Li-rich Mn-based layered oxides (LLO) cathode is hindered by severe capacity and voltage degradation resulting from severe oxygen release and irreversible phase transition. In this work, the reaction heterogeneity, which describes the spatially resolved electrochemical divergence within individual cathode particles, is engineered through compositional gradient design to couple Li + transport kinetics and the anion redox activity between particle interiors and surfaces. It is revealed that Co/Mn concentration gradient within particles creates heterogeneous phase content distribution and structural ordering, inducing surface-bulk reaction heterogeneity that significantly impacts the overall electrochemical performance. Specifically, Li 2 MnO 3 -poor and Co-enriched surface effectively mitigates the oxygen loss and enhances electrochemical reaction kinetics, benefited from the reduced surface redox reactivity and induced highly ordered intra-layered cationic arrangement. Meanwhile, the Li 2 MnO 3 -enriched core with slight Li/Ni intermixing provides high reversible capacity and strong mechanical stability. Consequently, the greatly enhanced anion redox reversibility, Li + diffusion dynamics, and structure stability endow LLO with exceptional electrochemical properties, showing a capacity retention of 86.0% and a reduced voltage decay of 0.518 mV per cycle after 500 cycles at 1 C. This work provides a valuable strategy to tailor the redox chemistry and achieve robust LLO.

25 ENERGY STORAGE↗

Fast-Charging and Ultrahigh-Capacity Lithium Metal Anode Enabled by Surface Alloying

Li metal anodes are going through a great revival but they still encounter grand challenges. One often neglected issue is that most reported Li metal anodes are only cyclable under relatively low current density (<5 mA cm -2 ) and small areal capacity (<5 mAh cm -2 ), which essentially limits their high-power applications and results in ineffective Li utilization (<1%). Herein, it is reported that surface alloyed Li metal anodes can enable reversible cycling with ultrafast rate and ultralarge areal capacity. Low-cost Si wafers are used and are chemically etched down to 20-30 mu m membranes. Simply laminating a Si membrane onto Li foil results in the formation of LixSi alloy film fused onto Li metal with mechanical robustness and high Li-ion conductivity. Symmetric cell measurements show that the surface alloyed Li anode has excellent cycling stability, even under high current density up to 25 mA cm -2 and unprecedented areal capacity up to 100 mAh cm -2 . Furthermore, the surface alloyed Li anode is paired with amorphous MoS 3 cathode and achieves remarkable full-cell performance.

36 MATERIALS SCIENCE↗

Anion-tethered Single Lithium-ion Conducting Polyelectrolytes through UV-induced Free Radical Polymerization for Improved Morphological Stability of Lithium Metal Anodes

Single Li + ion conducting polyelectrolytes (SICs), which feature covalently tethered counter-anions along their backbone, have the potential to mitigate dendrite formation by reducing concentration polarization and preventing salt depletion. However, due to their low ionic conductivity and complicated synthetic procedure, the successful validation of these claimed advantages in lithium metal (Li 0 ) anode batteries remains limited. In this study, we fabricated a SIC electrolyte using a single-step UV polymerization approach. The resulting electrolyte exhibited a high Li + transference number (t + ) of 0.85 and demonstrated good Li + conductivity (6.3×10 -5 S/cm at room temperature), which is comparable to that of a benchmark dual ion conductor (DIC, 9.1×10 -5 S/cm). Benefitting from the high transference number of SIC, it displayed a three-fold higher critical current density (2.4 mA/cm 2 ) compared to DIC (0.8 mA/cm 2 ) by successfully suppressing concentration polarization-induced short-circuiting. Additionally, the t + significantly influenced the deposition behavior of Li0, with SIC yielding a uniform, compact, and mosaic-like morphology, while the low t + DIC resulted in a porous morphology with Li 0 whiskers. Using the SIC electrolyte, Li 0 ||LiFePO 4 cells exhibited stable operation for 4500 cycles with 70.5 % capacity retention at 22 °C.

25 ENERGY STORAGE↗

Anion-tethered Single Lithium-ion Conducting Polyelectrolytes through UV-induced Free Radical Polymerization for Improved Morphological Stability of Lithium Metal Anodes

Single Li + ion conducting polyelectrolytes (SICs), which feature covalently tethered counter-anions along their backbone, have the potential to mitigate dendrite formation by reducing concentration polarization and preventing salt depletion. However, due to their low ionic conductivity and complicated synthetic procedure, the successful validation of these claimed advantages in lithium metal (Li 0 ) anode batteries remains limited. In this study, we fabricated a SIC electrolyte using a single-step UV polymerization approach. The resulting electrolyte exhibited a high Li + transference number (t + ) of 0.85 and demonstrated good Li + conductivity (6.3×10 -5 S/cm at room temperature), which is comparable to that of a benchmark dual ion conductor (DIC, 9.1×10 -5 S/cm). Benefitting from the high transference number of SIC, it displayed a three-fold higher critical current density (2.4 mA/cm 2 ) compared to DIC (0.8 mA/cm 2 ) by successfully suppressing concentration polarization-induced short-circuiting. Additionally, the t + significantly influenced the deposition behavior of Li 0 , with SIC yielding a uniform, compact, and mosaic-like morphology, while the low t + DIC resulted in a porous morphology with Li 0 whiskers. In conclusion, using the SIC electrolyte, Li 0 ||LiFePO 4 cells exhibited stable operation for 4500 cycles with 70.5 % capacity retention at 22 °C.

25 ENERGY STORAGE↗

Long–Cycling Sulfide–Based All–Solid–State Batteries Enabled by Electrochemo–Mechanically Stable Electrodes

Anode significantly determines the energy density of all-solid-state Lithium batteries (ASLBs). Silicon (Si) and Lithium (Li) metal are two of the most attractive anodes because of their ultrahigh theoretical capacities. However, most investigations focus on Li metal; the great potential of Si is underrated. This study investigates Si anode's stability, processability, and cost in ASLBs and compares them with Li metal. Moreover, the single-crystal LiNi 0.8 Co 0.1 Mn 0.1 O 2 is stabilized with a lithium silicate (Li 2 SiO x ) through a scalable sol-gel method. ASLBs with a cell-level energy density of 285 Wh kg -1 are obtained through sandwiching Si anode, thin sulfide solid-state electrolyte membrane, and interface stabilized LiNi 0.8 Co 0.1 Mn 0.1 O 2 . The full cell delivered a high capacity of 145 mAh g -1 at C/3 and maintained stability for 1000 cycles. This work inspires commercializing the ASLBs on a large scale with exciting manufacturing lines for large-scale, safe, and economical energy storage.

25 ENERGY STORAGE↗

Selective Lanthanide Sensing with Gold Nanoparticles and Hydroxypyridinone Chelators

The octadentate hydroxypyridinone chelator 3,4,3-LI(1,2-HOPO) is a promising therapeutic agent because of its high affinity for f-block elements and noncytotoxicity at medical dosages. The interaction between 3,4,3-LI(1,2-HOPO) and other biomedically relevant metals such as gold, however, has not been explored. Gold nanoparticles functionalized with chelators have demonstrated great potential in theranostics, yet thus far, no protocol that combines 3,4,3-LI(1,2-HOPO) and colloidal gold has been developed. Here, we characterize the solution thermodynamic properties of the complexes formed between 3,4,3-LI(1,2-HOPO) and Au 3+ ions and demonstrate how under specific pH conditions the chelator promotes the growth of gold nanoparticles, acting as both reducing and stabilizing agent. 3,4,3-LI(1,2-HOPO) ligands on the nanoparticle surface remain active and selective toward f-block elements, as evidenced by gold nanoparticle selective aggregation. Finally, a new colorimetric assay capable of reaching the detection levels necessary for the quantification of lanthanides in waste from industrial processes is developed based on the inhibition of particle growth by lanthanides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impacts of Lanthanum Impurities on Nickel-Rich Cathode Materials

The widespread use of lithium-ion batteries (LIBs) has led to environmental concerns and exacerbated the scarcity of essential minerals, underscoring the urgent need for effective recycling strategies. Among various recycling methods, the hydrometallurgical process is distinguished by its energy efficiency and minimal environmental impact. Nickel-metal hydride (Ni-MH) batteries are a significant source of nickel sulfate (NiSO 4 ) for hydrometallurgical recycling due to their substantial nickel content. A significant challenge arises from the effective separation of lanthanum (La), which results in at least 20 ppm of La being present in the recycled NiSO 4 . This study explores a critical aspect of the recycling process: the impact of La 3+ impurities, introduced through recycled NiSO 4 , on the performance of the synthesized nickel-rich cathode materials. We conducted a thorough investigation into how La 3+ influences morphology and structural integrity during both the synthesis of precursors and the production of cathode materials. Our findings indicate that La 3+ impurities do not adversely affect the morphology or structural integrity of the cathode precursors relative to virgin materials. However, higher concentrations of La 3+ reduce the discharge capacity with enhanced cycle stability by minimizing cation mixing between lithium (Li + ) and nickel (Ni 2+ ) ions within the cathode. Furthermore, this stability is crucial for extending battery life. Therefore, controlling the concentration of La 3+ impurities is essential for optimizing the electrochemical performance of recycled cathode materials.

Corrosion↗

Molecular Design of a Highly Stable Single-Ion Conducting Polymer Gel Electrolyte

Single-ion conducting (SIC) polymer electrolytes with a high Li transference number ( t Li + ) have shown the capability to enable enhanced battery performance and safety by avoiding liquid–electrolyte leakage and suppressing Li dendrite formation. However, issues of insufficient ionic conductivity, low electrochemical stability, and poor polymer/electrode interfacial contact have greatly hindered their commercial use. In this work, a Li-containing boron-centered fluorinated SIC polymer gel electrolyte (LiBFSIE) was rationally designed to achieve a high t Li + and high electrochemical stability. Owing to the low dissociation energy of the boron-centered anion and Li + , the as-prepared LiBFSIE exhibited an ionic conductivity of 2 × 10 –4 S/cm at 35 °C, which is exclusively contributed by Li ions owing to a high t Li + of 0.93. Both simulation and experimental approaches were applied to investigate the ion diffusion and concentration gradient in the LiBFSIE and non-cross-linked dual-ion systems. Typical rectangular Li stripping/plating voltage profiles demonstrated the uniform Li deposition assisted by LiBFSIE. The interfacial contact and electrolyte infiltration were further optimized with an in situ UV–vis-initiated polymerization method together with the electrode materials. By virtue of the high electrochemical stability of LiBFSIE, the cells achieved a promising average Coulombic efficiency of 99.95% over 200 cycles, which is higher than that of liquid–electrolyte-based cells. No obvious capacity fading was observed, indicating the long-term stability of LiBFSIE for lithium metal batteries.

36 MATERIALS SCIENCE↗

Interfacial solvation-structure regulation for stable Li metal anode by a desolvation coating technique

Rechargeable lithium (Li) metal batteries face challenges in achieving stable cycling due to the instability of the solid electrolyte interphase (SEI). The Li-ion solvation structure and its desolvation process are crucial for the formation of a stable SEI on Li metal anodes and improving Li plating/stripping kinetics. This research introduces an interfacial desolvation coating technique to actively modulate the Li-ion solvation structure at the Li metal interface and regulate the participation of the electrolyte solvent in SEI formation. Through experimental investigations conducted using a carbonate electrolyte with limited compatibility to Li metal, the optimized desolvation coating layer, composed of 12-crown-4 ether-modified silica materials, selectively displaces strongly coordinating solvents while simultaneously enriching weakly coordinating fluorinated solvents at the Li metal/electrolyte interface. This selective desolvation and enrichment effect reduce solvent participation to SEI and thus facilitate the formation of a LiF-dominant SEI with greatly reduced organic species on the Li metal surface, as conclusively verified through various characterization techniques including XPS, quantitative NMR, operando NMR, cryo-TEM, EELS, and EDS. The interfacial desolvation coating technique enables excellent rate cycling stability (i.e., 1C) of the Li metal anode and prolonged cycling life of the Li||LiCoO 2 pouch cell in the conventional carbonate electrolyte (E/C 2.6 g/Ah), with 80% capacity retention after 333 cycles.

42 ENGINEERING↗

Polymer-Stabilized Liquid Metal Nanoparticles as a Scalable Current Collector Engineering Approach Enabling Lithium Metal Anodes

Dendrites and dead lithium formation over prolonged cycling have long been challenges that hinder the safe implementation of metallic Li anodes. In this study, we employ polymer-stabilized liquid metal nanoparticles (LM-P NPs) of eutectic gallium indium (EGaIn) to create uniform Li nucleation sites enabling homogeneous lithium electrodeposition. Block copolymers of poly(ethylene oxide) and poly(acrylic acid) (PEO-b-PAA) were grafted onto the EGaIn surface, forming stabilized, well-dispersed NPs. Using a scalable spray coating approach, LM-P NPs were fabricated on copper current collectors, providing lithiophilic PEO sites and interactive carboxyl groups to guide Li deposition. The Li-EGaIn alloying process greatly reduced the Li + diffusion barrier, enabling fast Li transport through the coating layer, resulting in decreased nucleation overpotential. Therefore, about five times lower Li nucleation overpotential was obtained on the LM-P modified Cu with an optimal composition of the polymers than the bare Cu substrates. DFT computations was used to reveal the binding properties between the LM-P layer and Li. Due to the regulated Li plating/stripping process, as-obtained 30 μm Li anodes paired with LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM8 11 ) with a negative/positive electrode capacity (N/P) ratio ~ 10 exhibited stable cycling performance at 0.5C for over 250 cycles, with an average Coulombic efficiency of 99.55%. Ultrathin Li (1 μm) anodes with an N/P ratio ~ 0.6 were also demonstrated in Li|LiFePO 4 cells, which examined the stabilization of Li by LM-P NPs and monitored practical loadings of Li anodes that are close to anode-free systems.

25 ENERGY STORAGE↗

Coherent Strain-Inhibiting Phase Construction of Lithium-Rich Manganese-Based Oxide Toward High Mechanochemical Stability

A layered lithium-rich manganese-based oxide cathode, containing $R\overline{3}m$ (LiTMO 2 , TM = Mn, Ni, Co) and $C2/m$ (Li 2 MnO 3 ) nanodomains, utilizes both transition metals and oxygen redox to yield substantial energy density. However, the inherent heterogeneous nature and distinct nanodomain redox chemistries of layered lithium-rich oxides will inevitably cause pernicious lattice strain and structural displacement, which can hardly be eliminated by conventional doping or coating strategies and result in accelerated performance decay. Herein, we incorporate a strain-inhibiting perovskite phase coherently grown within the layered structure to effectively restrain the displacement and lattice strain during uneven Li-ion extraction. The enhanced mechanochemical stability of the designed cathode benefits the persistent structure and reversible oxygen redox, thereby achieving high initial Coulombic efficiency and stable cycling and voltage profiles. In conclusion, our approach of lattice engineering alleviates the strain and displacement caused by inhomogeneous reactivity between heterogeneous nanodomains and promotes the development of advanced cathode materials with long durability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparative Analysis of Reactivity of Al and Ga Doped Garnet Solid State Electrolyte at the Interface with Li Metal

Lithium garnet (Li 7 La 3 Zr 2 O 12 , LLZO) based solid electrolytes are leading candidate materials for all-solid-state batteries with lithium metal anodes because of their high ionic conductivity, high mechanical toughness, and superior electrochemical stability. While doping LLZO with Al and Ga increases its ionic conductivity by stabilizing the cubic phase, the impact of dopants on its (electro)chemical stability at the interfaces with Li metal is critical. Here, our study of differences between Al- and Ga-doped LLZO when interfaced with lithium metal using X-ray photoelectron spectroscopy and density functional theory shows a higher propensity of Ga to move across LLZO interface with Li metal and form Ga-Li alloy. Additionally, neutron diffraction reveals loss of cubic phase resulting from the loss of dopant that explains electrochemical behavior differences between Ga- and Al-doped LLZO. Overall, our study reveals the key role of dopant chemistry in enabling stable solid electrolyte materials for all-solid-state batteries.

Klenk, Matthew↗

Highly Conductive Polyoxanorbornene‐Based Polymer Electrolyte for Lithium‐Metal Batteries

Abstract This present study illustrates the synthesis and preparation of polyoxanorbornene‐based bottlebrush polymers with poly(ethylene oxide) (PEO) side chains by ring‐opening metathesis polymerization for solid polymer electrolytes (SPE). In addition to the conductive PEO side chains, the polyoxanorbornene backbones may act as another ion conductor to further promote Li‐ion movement within the SPE matrix. These results suggest that these bottlebrush polymer electrolytes provide impressively high ionic conductivity of 7.12 × 10 −4 S cm −1 at room temperature and excellent electrochemical performance, including high‐rate capabilities and cycling stability when paired with a Li metal anode and a LiFePO 4 cathode. The new design paradigm, which has dual ionic conductive pathways, provides an unexplored avenue for inventing new SPEs and emphasizes the importance of molecular engineering to develop highly stable and conductive polymer electrolytes for lithium‐metal batteries (LMB).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interfacial engineering for stabilizing polymer electrolytes with 4V cathodes in lithium metal batteries at elevated temperature

Poly (ethylene oxide) (PEO) polymer electrolytes are promising candidates for next-generation rechargeable lithium batteries. However, the poor interfacial stability between 4 V cathodes and PEO electrolytes impedes their applications in 4 V lithium batteries with high energy density. Here, we demonstrate a facile and effective strategy to enhance the interfacial stability by the synergy of Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) coating on the cathode surface, and salt combination in the electrolyte, even with a cut-off voltage of 4.25–4.4 V vs. Li + /Li. Nano-LAGP coated Li|PEO|LiCoO 2 cell delivers stable cycling with a capacity retention of 81.9%/400 cycles and 84.7%/200 cycles at 60 °C when charged to 4.25 and 4.3 V in pure polyether electrolyte, respectively. Steady cycling is also demonstrated at room temperature and with LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523) cathode. This work offers a viable and scalable approach to improve the stability between PEO electrolytes and 4 V cathodes and open up new possibilities for practical application of 4 V lithium metal batteries.

25 ENERGY STORAGE↗

Dimer Acceptor Adopting a Flexible Linker for Efficient and Durable Organic Solar Cells

Abstract Organic solar cells (OSCs) have advanced rapidly due to the development of new photovoltaic materials. However, the long‐term stability of OSCs still poses a severe challenge for their commercial deployment. To address this issue, a dimer acceptor ( d T9TBO) with flexible linker is developed for incorporation into small‐molecule acceptors to form molecular alloy with enhanced intermolecular packing and suppressed molecular diffusion to stabilize active layer morphology. Consequently, the PM6 : Y6 : d T9TBO‐based device displays an improved power conversion efficiency (PCE) of 18.41 % with excellent thermal stability and negligible decay after being aged at 65 °C for 1800 h. Moreover, the PM6 : Y6 : d T9TBO‐based flexible OSC also exhibits excellent mechanical durability, maintaining 95 % of its initial PCE after being bended repetitively for 1500 cycles. This work provides a simple and effective way to fine‐tune the molecular packing with stabilized morphology to overcome the trade‐off between OSC efficiency and stability.

Chemistry↗

Dual Enhancement of Thermostability and Activity of Xylanase through Computer-Aided Rational Design

In the realm of enzyme engineering, the dual enhancement of thermostability and activity remains a challenge. Herein, we employed a computer-aided approach integrating folding free energy calculations and evolutionary analysis to engineer Paecilomyces thermophila xylanase into a hyperthermophilic enzyme for application in the paper and pulp industry. Through the computational rational design, XynM9 with superior thermostability and enhanced activity was designed. Its optimal reaction temperature increases by 10 °C to 85 °C, its T m increases by 10 °C to 93 °C, and its half-life increases 11-fold to 5.8 h. Additionally, its catalytic efficiency improves by 57% to 3926 s –1 mM –1 . Molecular dynamics simulations revealed that XynM9 is stabilized by more hydrogen bonds and salt bridges than wild-type xylanase. The mutant’s narrower catalytic cleft enhances the substrate-binding affinity, thus improving the catalytic efficiency. In harsh conditions at 80 °C and pH 10, using XynM9 significantly reduced both hemicellulose and lignin, which makes it a good candidate for use in the paper and pulp process. Finally, our study presents an accurate and efficient strategy for the dual enhancement of enzyme properties, guiding further improvement of computational tools for protein stabilization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of particle size and particle-flow-wall coupling on pressurized oxy-combustion in the down-fired burner

Concerns over climate change have led to numerous efforts in developing low-carbon energy technologies. Pressurized oxy-combustion (POC) is a promising candidate to reduce carbon emissions in power generation. Designing an effective burner plays a vital role in developing new coal combustion technologies. Because of the high pressure, the volume fraction of coal particles at the fuel inlet of the burner of a pressurized oxy-combustor is close or even higher than the maximum limit that commercial CFD codes (e.g., ANSYS FLUENT) can handle. At this high particle volume fraction, the interactions among particles, fluid flow, and wall need to be re-evaluated. The present computational work is the first step of a systematic analysis of the particle influence, like releasing method, releasing locating, and particle size, in a pilot-scale POC combustor, developed at Washington University in St. Louis (WUSTL). In a POC process, pulverized coal is burned under elevated pressure and O2-CO2 environment. Specifically, a 15-bar, 100 kWth, POC combustor is modeled employing ANSYS FLUENT, using Reynolds-averaged Navier-Stokes (RANS) modeling. It is revealed that for this pilot-scale, pressurized burner, velocity profiles of the near-wall region in this POC facility exhibit some discrepancy against the near-wall turbulent flow velocity profile. In order to investigate the particle influence in the near-wall region, particle releasing location will be investigated. Numerical simulation results exhibit the coupling effect of turbulence flow and particles in this case. The particle size also demonstrates a great effect on particle trajectory, then further has an impact on flame stability and temperature.

Li, Lei↗