Two-Dimensional Electrolyte Design: Broadening the Horizons of Functional Electrolytes in Lithium Batteries.

ConspectusSince their commercialization in the 1990s, lithium-ion batteries (LIBs) have been increasingly used in applications such as portable electronics, electric vehicles, and large-scale energy storage. The increasing use of LIBs in modern society has necessitated superior-performance LIB development, including electrochemical reversibility, interfacial stability, efficient kinetics, environmental adaptability, and intrinsic safety, which is difficult to simultaneously achieve in commercialized electrolytes. Current electrolyte systems contain a solution with Li salts (e.g., LiPF6) and solvents (e.g., ethylene carbonate and dimethyl carbonate), in which the latter dissolves Li salts and strongly interacts with Li+ (lithiophilic feature). Only lithiophilic agents can be functionally modified (e.g., additives and solvents), altering the bulk and interfacial behaviors of Li+ solvates. However, such approaches alter pristine Li+ solvation and electrochemical processes, making it difficult to strike a balance between the electrochemical performance and other desired electrolyte functions. This common electrolyte design in lithiophilic solvents shows strong coupling among formulation, coordination, electrochemistry, and electrolyte function. The invention of lithiophobic cosolvents (e.g., multifluorinated ether and fluoroaromatic hydrocarbons) has expanded the electrolyte design space to lithiophilic (interacts with Li+) and lithiophobic (interacts with solvents but not with Li+) dimensions. Functional modifications switch to lithiophobic cosolvents, affording superior properties (carried by lithiophobic cosolvents) with little impact on primary Li+ solvation (dictated by lithiophilic solvents). This electrolyte engineering technique based on lithiophobic cosolvents is the 2D electrolyte (TDE) principle, which decouples formulation, coordination, electrochemistry, and function. The molecular-scale understanding of TDEs is expected to accelerate electrolyte innovations in next-generation LIBs.This Account provides insights into recent advancements in electrolytes for superior LIBs from the perspective of lithiophobic agents (i.e., lithiophobic additives and cosolvents), establishing a generalized TDE principle for functional electrolyte design. In bulk electrolytes, a microsolvating competition emerges because of cosolvent-induced dipole-dipole and ion-dipole interactions, forming a loose solvation shell and a kinetically favorable electrolyte. At the electrode/electrolyte interface, the lithiophobic cosolvent affords reliable passivation and efficient desolvation, with interfacial compatibility and electrochemical reversibility even under harsh conditions. Based on this unique coordination chemistry, functional electrolytes are formulated without significantly sacrificing their electrochemical performance. First, lithiophobic cosolvents are used to tune Li+-solvent affinity and anion mobility, promoting Li+ diffusion and electrochemical kinetics of the electrolyte to benefit high-rate and low-temperature applications. Second, the lithiophobic cosolvent undergoes less thermally induced decomposition and constructs a thermally stable interphase in TDEs, affording electrolytes with high-temperature adaptability and cycling stability. Third, the lithiophobic cosolvent modifies the local Li+-solvent-anion topography, controlling electrolyte electrochemical reversibility to afford numerous promising solvents that cannot be used in common electrolyte design. Finally, the lithiophobic cosolvent mitigates detrimental crosstalk between flame retardants and carbonate solvents, improving the intrinsic electrolyte safety without compromising electrochemical performance, which broadens the horizons of electrolyte design by optimizing versatile cosolvents and solvents, inspiring new ideas in liquid electrochemistry in other battery systems.

Switching Reaction Pathway of Medium-Concentration Ether Electrolytes to Achieve 4.5 V Lithium Metal Batteries.

Pursuing high-energy-density lithium metal batteries (LMBs) necessitates the advancement of electrolytes. Despite demonstrating high compatibility with lithium metal anodes (LMAs), ether-based electrolytes face challenges in achieving stable cycling at high voltages. Herein, we propose a strategy to enhance the high-voltage stability of medium-concentration (∼1 M) ether electrolytes by altering the reaction pathway of ether solvents. By employing a 1 M lithium difluoro(oxalato)borate in dimethoxyethane (LiDFOB/DME) electrolyte, we observed that LiDFOB displays a pronounced tendency for decomposition over DME, leading to a modification in the decomposition pathway of DME. This modification facilitates the formation of a stable organic-inorganic hybrid interface. Utilizing such an electrolyte, the Li-LCO cell demonstrates a discharge specific capacity of 146 mAh g-1 (5 C) and maintains retention of 86% over 1000 cycles at 2 C under a 4.5 V cutoff voltage. Additionally, the optimized ether electrolyte demonstrated outstanding cycling performance in Li-LCO full cells under practical conditions.

Comparison of multi-mode Hong-Ou-Mandel interference and multi-slit interference.

Hong-Ou-Mandel (HOM) interference of multi-mode frequency entangled states plays a crucial role in quantum metrology. However, as the number of modes increases, the HOM interference pattern becomes increasingly complex, making it challenging to comprehend intuitively. To overcome this problem, we present the theory and simulation of multi-mode-HOM interference (MM-HOMI) and compare it to multi-slit interference (MSI). We find that these two interferences have a strong mapping relationship and are determined by two factors: the envelope factor and the details factor. The envelope factor is contributed by the single-mode HOM interference (single-slit diffraction) for MM-HOMI (MSI). The details factor is given by sin (Nx)/sin (x) ([sin (Nv)/sin (v)]2) for MM-HOMI (MSI), where N is the mode (slit) number and x (v) is the phase spacing of two adjacent spectral modes (slits). As a potential application, we demonstrate that the square root of the maximal Fisher information in MM-HOMI increases linearly with the number of modes, indicating that MM-HOMI is a powerful tool for enhancing precision in time estimation. We also discuss multi-mode Mach-Zehnder interference, multi-mode NOON-state interference, and the extended Wiener-Khinchin theorem. This work may provide an intuitive understanding of MM-HOMI patterns and promote the application of MM-HOMI in quantum metrology.

Spatial-spectral mapping to prepare frequency entangled qudits.

Entangled qudits, the high-dimensional entangled states, play an important role in the study of quantum information. How to prepare entangled qudits in an efficient and easy-to-operate manner is still a challenge in quantum technology. Here, we demonstrate a method to engineer frequency entangled qudits in a spontaneous parametric downconversion process. The proposal employs an angle-dependent phase-matching condition in a nonlinear crystal, which forms a classical-quantum mapping between the spatial (pump) and spectral (biphotons) degrees of freedom. In particular, the pump profile is separated into several bins in the spatial domain, and thus shapes the down-converted biphotons into discrete frequency modes in the joint spectral space. Our approach provides a feasible and efficient method to prepare a high-dimensional frequency entangled state. As an experimental demonstration, we generate a three-dimensional entangled state by using a homemade variable slit mask.

Passivating Lithiated Graphite via Targeted Repair of SEI to Inhibit Exothermic Reactions in Early-Stage of Thermal Runaway for Safer Lithium-Ion Batteries.

The self-exothermic in early stage of thermal runaway (TR) is blasting-fuse for Li-ion battery safety issues. The exothermic reaction between lithiated graphite (LiCx ) and electrolyte accounts for onset of this behavior. However, preventing the deleterious reaction still encounters hurdles. Here, we manage to inhibit this reaction by passivating LiCx in real time via targeted repair of SEI. It is shown that 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane (D3 F) can be triggered by LiCx to undergo ring-opening polymerization at elevated temperature, so as to targeted repair of fractured SEI. Due to the high thermal stability of polymerized D3 F, exothermic reaction between LiCx and electrolyte is inhibited. As a result, the self-exothermic and TR trigger temperatures of pouch cell are increased from 159.6 and 194.2 °C to 300.5 and 329.7 °C. This work opens up a new avenue for designing functional additives to block initial exothermal reaction and inhibit TR in early stage.

Cyclopentylmethyl Ether, a Non-Fluorinated, Weakly Solvating and Wide Temperature Solvent for High-Performance Lithium Metal Battery.

While recent work demonstrates the advantages of weakly solvating solvents in enhancing the cyclability of LMBs, both new designs and design strategies for high performance weakly solvating solvent, especially physicochemical properties, are still lacking. Here, we propose a molecular design to tune the solvating power and physicochemical properties of non-fluorinated ether solvent. The resulting cyclopentylmethyl ether (CPME) have a weak solvating power and wide liquid-phase temperature range. By optimizing the salt concentration, the CE is further promoted to 99.4 %. Besides, the improved electrochemical performance of Li-S battery in CPME-based electrolytes is obtained at -20 °C. The Li||LFP (17.6 mg cm-2 ) battery with developed electrolyte maintains >90 % of the original capacity over 400 cycles. Our design concept for solvent molecule provides a promising pathway to non-fluorinated electrolytes with weakly solvating power and wide temperature window for high-energy-density LMBs.

Nanophase-Separated, Elastic Epoxy Composite Thin Film as an Electrolyte for Stable Lithium Metal Batteries.

The design of solid polymer electrolytes (SPE) with high ionic conductivity and excellent mechanical properties is challenging because these two properties are often conflicting. To achieve both, a reaction-controlled strategy is proposed based on the nanophase separation of an ionic transport pathway and a supporting matrix to balance ionic mobility and mechanical properties. Specifically, an elastic epoxy polymer electrolyte (eEPE), synthesized via two-step polymerization, combines outstanding mechanical strength (toughness of 3.4 MJ m-3) and high ionic conductivity (3.5 × 10-4 S cm-1 at 25 °C). The nanostructured eEPE is both tough and flexible, therefore promotes uniform deposition of Li even under a high current density (2 mA cm-2 and 2 mAh cm-2). Importantly, eEPE composite films greatly improve the safety performance of the LiFePO4/Li pouch cells: safe operations are achieved under several abusive conditions. This work highlights an alternative route for high-safety solid-state lithium metal batteries of the next generation.

Nitrofullerene, a C60-based Bifunctional Additive with Smoothing and Protecting Effects for Stable Lithium Metal Anode.

Practical applications of lithium metal anodes are gravely impeded by inhomogeneous lithium deposition, which results in dendrite growth. Electrolyte additives are proven to be effective in improving performance but usually serve only a single function. Herein, nitrofullerene is introduced as a bifunctional additive with a smoothing effect and forms a protective solid electrolyte interphase (SEI) layer on stable lithium metal anodes. By design, nitro-C60 can gather on electrode protuberances via electrostatic interactions and then be reduced to NO2- and insoluble C60. Next, the C60 anchors on the uneven groove of the lithium surface, resulting in a homogeneous distribution of Li ions. Finally, NO2- anions can react with metallic Li to build a compact and stable SEI with high ion transport. With a 5 mM nitro-C60 additive, Li-Li symmetric cells show superior cycle stability in both carbonate and ether electrolytes, Li-sulfur batteries with a high cathode loading (10.6 mg cm-2, 6 mAh cm-2) can achieve improved cycle retention of 63.2% over 100 cycles in a carbonate electrolyte, and full cells paired with a high-areal-capacity LiNi0.6Co0.2Mn0.2O2 cathode (3.5 mAh cm-2) exhibit a significantly enhanced cycle lifespan even under lean electrolyte conditions.

Facile Generation of Polymer-Alloy Hybrid Layers for Dendrite-Free Lithium-Metal Anodes with Improved Moisture Stability.

Lithium-metal anodes are recognized as the most promising next-generation anodes for high-energy-storage batteries. However, lithium dendrites lead to irreversible capacity decay in lithium-metal batteries (LMBs). Besides, the strict assembly-environment conditions of LMBs are regarded as a challenge for practical applications. In this study, a workable lithium-metal anode with an artificial hybrid layer composed of a polymer and an alloy was designed and prepared by a simple chemical-modification strategy. Treated lithium anodes remained dendrite-free for over 1000 h in a Li-Li symmetric cell and exhibited outstanding cycle performance in high-areal-loading Li-S and Li-LiFePO4 full cells. Moreover, the treated lithium showed improved moisture stability that benefits from the hydrophobicity of the polymer, thus retaining good electrochemical performance after exposure to humid air.

4-Fluorobenzyl cyanide, a sterically-hindered solvent expediting interfacial kinetics in lithium-ion batteries.

The electrochemical performance of lithium-ion batteries (LIBs) is plagued by sluggish interfacial kinetics. Fortunately, the Li+ solvation structure bridges the bulk electrolyte and interfacial chemistry, providing a pathway for promoting electrochemical kinetics in LIBs. Herein, we improve the interfacial kinetics by tuning the Li+ coordination chemistry based on solvent molecular engineering. Specifically, 4-fluorobenzyl cyanide (FBCN), featuring steric hindrance and a weak Lewis basic center, is designed to construct a bulky coordination structure with Li+, weakening ion-dipole interaction (Li+-solvents) but promoting coulombic attraction (Li+-anions) at a normal Li salt concentration. This sterically-controlled solvation chemistry reduces the interfacial barrier and thus contributes to improved rate performance, as demonstrated practically in LiFePO4//graphite pouch cells. This study provides fresh insights into solvent steric control and coordination chemistry engineering, opening a new avenue for enhancing electrochemical kinetics in LIBs.

Elevated TRPV2 expression in the facial nerve of rats by cold stimulation: Implications for Bell's palsy.

OBJECTIVE: Bell's palsy, also referred to as clinical manifestations of unilateral facial nerve palsy, encompasses downward angling of the corners of the mouth, the absence of forehead creases, and unilateral incomplete eyelid closure. The incidence of Bell's palsy has increased progressively in recent years, but the underlying mechanism of its occurrence remains unknown; therefore, it is essential to investigate both the cause and treatment of Bell's palsy. Member 2 of the Subfamily V Transient Receptor Potential Cation Channel is a mechanically and thermally sensitive ion channel that plays a crucial role in neural growth and development. Using a novel modeling technique, we endeavored to develop an animal model of Bell's palsy and determine whether TRPV2 expression is altered throughout the course of a facial nerve injury. MATERIALS AND METHODS: The rats were categorized into 3 groups, and their facial nerve function was assessed using RT-qPCR, WB, and pathologic testing, respectively, after undergoing unilateral cold air stimulation for 1, 3, and 7 days. TRPV2 expression was identified using these techniques. RESULTS: In response to cold stimulation, rats exhibited facial nerve paralysis symptoms, demyelinating lesions in the facial nerve, and increased TRPV2 expression. CONCLUSIONS: Extended cold stimulation of the facial nerve in rats may lead to an imbalance in facial nerve homeostasis and increased TRPV2 expression. These findings will contribute to the understanding of the potential mechanism by which cold stimulation affects the facial nerve. Moreover, this finding implies that TRPV2 could possibly function as an additional diagnostic marker or therapeutic target in the context of Bell's palsy.

Direct lithium extraction from spent batteries for efficient lithium recycling.

The flourishing expansion of the lithium-ion batteries (LIBs) market has led to a surge in the demand for lithium resources. Developing efficient recycling technologies for imminent large-scale retired LIBs can significantly facilitate the sustainable utilization of lithium resources. Here, we successfully extract active lithium from spent LIBs through a simple, efficient, and low-energy-consumption chemical leaching process at room temperature, using a solution comprised of polycyclic aromatic hydrocarbons and ether solvents. The mechanism of lithium extraction is elucidated by clarifying the relationship between the redox potential and extraction efficiency. More importantly, the reclaimed active lithium is directly employed to fabricate LiFePO4 cathode with performance comparable to commercial materials. When implemented in 56 Ah prismatic cells, the cells deliver stable cycling properties with a capacity retention of ∼90% after 1200 cycles. Compared with the other strategies, this technical approach shows superior economic benefits and practical promise. It is anticipated that this method may redefine the recycling paradigm for retired LIBs and drive the sustainable development of industries.

scATAnno: Automated Cell Type Annotation for single-cell ATAC Sequencing Data.

Recent advances in single-cell epigenomic techniques have created a growing demand for scATAC-seq analysis. One key analysis task is to determine cell type identity based on the epigenetic data. We introduce scATAnno, a python package designed to automatically annotate scATAC-seq data using large-scale scATAC-seq reference atlases. This workflow generates the reference atlases from publicly available datasets enabling accurate cell type annotation by integrating query data with reference atlases, without the use of scRNA-seq data. To enhance annotation accuracy, we have incorporated KNN-based and weighted distance-based uncertainty scores to effectively detect cell populations within the query data that are distinct from all cell types in the reference data. We compare and benchmark scATAnno against 7 other published approaches for cell annotation and show superior performance in multiple data sets and metrics. We showcase the utility of scATAnno across multiple datasets, including peripheral blood mononuclear cell (PBMC), Triple Negative Breast Cancer (TNBC), and basal cell carcinoma (BCC), and demonstrate that scATAnno accurately annotates cell types across conditions. Overall, scATAnno is a useful tool for scATAC-seq reference building and cell type annotation in scATAC-seq data and can aid in the interpretation of new scATAC-seq datasets in complex biological systems.

Visible-light photocatalytic radical alkenylation of α-carbonyl alkyl bromides and benzyl bromides.

Through the use of [Ru(bpy)3Cl2] (bpy=2,2'-bipyridine) and [Ir(ppy)3] (ppy=phenylpyridine) as photocatalysts, we have achieved the first example of visible-light photocatalytic radical alkenylation of various α-carbonyl alkyl bromides and benzyl bromides to furnish α-vinyl carbonyls and allylbenzene derivatives, prominent structural elements of many bioactive molecules. Specifically, this transformation is regiospecific and can tolerate primary, secondary, and even tertiary alkyl halides that bear ß-hydrides, which can be challenging with traditional palladium-catalyzed approaches. The key initiation step of this transformation is visible-light-induced single-electron reduction of C-Br bonds to generate alkyl radical species promoted by photocatalysts. The following carbon-carbon bond-forming step involves a radical addition step rather than a metal-mediated process, thereby avoiding the undesired ß-hydride elimination side reaction. Moreover, we propose that the Ru and Ir photocatalysts play a dual role in the catalytic system: they absorb energy from the visible light to facilitate the reaction process and act as a medium of electron transfer to activate the alkyl halides more effectively. Overall, this photoredox catalysis method opens new synthetic opportunities for the efficient alkenylation of alkyl halides that contain ß-hydrides under mild conditions.

1,3,5-Trifluorobenzene, an electrolyte additive with high thermal stability and superior film-forming properties for lithium-ion batteries.

The introduction of 1,3,5-trifluorobenzene (F3B) as an additive for lithium-ion battery electrolytes can produce a LiF-rich solid electrolyte interface (SEI). Meanwhile, F3B has superior thermal stability compared with traditional fluorinated additives and is less likely to produce hydrogen fluoride to damage the cathode.

Association between dietary intake of omega-3 polyunsaturated fatty acids and all-cause and cardiovascular mortality among hypertensive adults: Results from NHANES 1999-2018.

BACKGROUND: Hypertensive adults are at a higher risk of cardiovascular morbidity and mortality. Dietary omega-3 polyunsaturated fatty acids (N3-PUFA) intake has been associated with cardiovascular benefits. However, few studies have specifically investigated whether dietary intake of N3-PUFA is associated with lower risk of all-cause and cardiovascular mortality among hypertensive adults in the U.S. METHODS: This prospective cohort study included 26,914 hypertensive individuals 18 years or older who participated in 10 NHANES cycles from 1999 to 2018. Dietary levels of N3-PUFA were obtained from the 24-hour dietary recalls. The dietary data were linked to mortality records from the National Death Index through December 31, 2019. The associations between dietary N3-PUFA levels and mortality were evaluated by constructing the Multivariable Cox Proportional Hazards models. RESULTS: We observed an increasing trend of dietary N3-PUFA intake levels over the years, mainly driven by alpha-linolenic acid (ALA). Lower all-cause mortality risk was observed among hypertensive adults with higher consumption of total N3-PUFA [adjusted hazards ratio, 95% confidence interval: 0.91 (0.86, 0.97)], plant-based ALA [0.88 (0.83, 0.93)], fish oil-based eicosapentaenoic acid (EPA) + docosahexaenoic acid (DHA) [0.91 (0.83, 0.99)], EPA [0.93 (0.88, 0.98)], docosapentaenoic acid (DPA) [0.73 (0.58, 0.91)], or DHA [0.95 (0.90, 0.99)]. Hypertensive adults were at lower risk of cardiovascular mortality if their diet contained higher levels of total N3-PUFA [0.68 (0.53, 0.88)], ALA [0.89 (0.80, 0.99)], EPA [0.87 (0.79, 0.97)] or DPA [0.86 (0.78, 0.95)]. Weighted quantile sum analysis showed that ALA, EPA, and DPA were the main contributors of the N3-PUFA benefits against mortality among hypertensive adults. CONCLUSIONS: Dietary intake of N3-PUFA, particularly ALA, EPA, and DPA, was associated with lower risk of all-cause and cardiovascular mortality among U.S. hypertensive adults. These findings suggest that increasing dietary intake of N3-PUFA may serve as a potential strategy to lower hypertension-associated mortality risk.

Revealing Surfactant Effect of Trifluoromethylbenzene in Medium-Concentrated PC Electrolyte for Advanced Lithium-Ion Batteries.

Despite wide-temperature tolerance and high-voltage compatibility, employing propylene carbonate (PC) as electrolyte in lithium-ion batteries (LIBs) is hampered by solvent co-intercalation and graphite exfoliation due to incompetent solvent-derived solid electrolyte interphase (SEI). Herein, trifluoromethylbenzene (PhCF3 ), featuring both specific adsorption and anion attraction, is utilized to regulate the interfacial behaviors and construct anion-induced SEI at low Li salts' concentration (<1 m). The adsorbed PhCF3 , showing surfactant effect on graphite surface, induces preferential accumulation and facilitated decomposition of bis(fluorosulfonyl)imide anions (FSI- ) based on the adsorption-attraction-reduction mechanism. As a result, PhCF3 successfully ameliorates graphite exfoliation-induced cell failure in PC-based electrolyte and enables the practical operation of NCM613/graphite pouch cell with high reversibility at 4.35 V (96% capacity retention over 300 cycles at 0.5 C). This work constructs stable anion-derived SEI at low concentration of Li salt by regulating anions-co-solvents interaction and electrode/electrolyte interfacial chemistries.

Influence of cold-stimulated adipocyte supernatant on the expression of adhesion-related molecules in Schwann cell line.

Bell's palsy is the most common form of facial nerve palsy. This study aimed to explore the pathogenesis of Bell's palsy by investigating the effect of cold-stimulated adipocyte supernatant on adhesion molecule expression in Schwann cell line. Schwann cells were cultured in regular or adipocyte-conditioned medium and analyzed using RNA sequencing. The mRNA expression of Schwann cell adhesion molecules melanoma cell adhesion molecule (MCAM), protocadherin 9 (PCDH9), and intercellular cell adhesion molecule 1 (ICAM1) was determined using real-time reverse-transcription polymerase chain reaction. Differentially expressed genes were identified, and Gene Ontology and Kyoto Encyclopedia of Genes and Genomes pathway enrichment analyses were conducted. Compared with Schwann cells in 37 °C, the expression of MCAM, PCDH9, and ICAM1 was downregulated in Schwann cells treated with cold-stimulated adipocyte supernatant compared with Schwann cells in 37 °C. Adipocytes subjected to cold exposure may weaken the adhesion capacity of Schwann cells and disrupt the local homeostasis of Schwann cell-axon interactions by affecting the expression of MCAM, PCDH9, and ICAM1, ultimately leading to the development of demyelinating lesions.

Bell's palsy was associated with TRPV2 downregulation of Schwann cell by cold stress.

OBJECTIVE: Epidemiological and clinical studies have shown that sharp changes in the ambient temperature are associated with the occurrence and development of Bell's palsy. However, the specific pathogenesis of peripheral facial paralysis remains nebulous. This study investigated the effect of cold stress on transient receptor potential cation channel subfamily V member 2 (TRPV2) secretion by Schwann cells and its role in Bell's palsy. MATERIALS AND METHODS: Schwann cell morphology was observed using transmission electron microscopy (TEM). Cell proliferation, apoptosis and cell cycle were analysed using CCK8 and flow cytometry. ELISA, Reverse transcription-quantitative PCR, western blotting and immunocytochemical fluorescence staining were used to detect the effects of cold stress on TRPV2, neural cell adhesion molecule (NCAM) and nerve growth factor (NGF) expression in Schwann cells. RESULTS: Cold stress resulted in a widening of the intercellular space, and the particles on the membrane showed different degrees of loss. Cold stress may cause Schwann cells to enter a cold dormant state. ELISA, RT-qPCR, western blotting and immunocytochemical fluorescences staining indicated that cold stress inhibited the expression of TRPV2, NCAM, and NGF. CONCLUSIONS: Drastic temperature difference between cold and heat can downregulate TRPV2 and the secretome of Schwann cells. The imbalance of Schwann cell homeostasis under such stress may contribute to nerve signalling dysfunction leading to the development of facial paralysis.