Hydrogen Bond Boosted Ferroelectric Polarization Enables High Rate Capability Lithium Metal Batteries.

Lithium metal is considered as a promising anode material for next generation lithium-based batteries due to its highest specific capacity and lowest reduction potential. However, irreversible lithium stripping/depositing gives rise to severe dendritic growth and countless dead lithium, which lead to rapid electrochemical performance degradation and increased safety hazards, and thus limit its large-scale application. Herein, this work demonstrates a universal hydrogen-bond-induced strategy to in situ form a highly polarized ferroelectric polyvinylidene fluoride (PVDF) coating on the anode current collector. The localized electric field induced by the polarized ferroelectric PVDF can accelerate the migration of lithium ions and alleviate the shortage of lithium ions and uneven ion/electron distribution and transfer at the anode/electrolyte interface, thus promoting uniform deposition and stripping of Li+ at high-rate situations. As a result, the symmetrical Li || Li batteries with polarized PVDF coating exhibit a long cycling lifespan over 900 h under 2 mA cm-2 with marginal voltage polarization, and an ultra-high-rate performance up to 8.85 mA cm-2 . The full cells using LiFePO4 cathode also display enhanced electrochemical performance. The innovative strategy of ferroelectric polarization sheds light on interface engineering to circumvent Li dendrite growth in lithium metal batteries (LMBs).

Nanoflower-like NiCo2O4 Composite Graphene Oxide as a Bifunctional Catalyst for Zinc-Air Battery Cathode.

Developing efficient bifunctional catalysts for nonprecious metal-based oxygen reduction (ORR) and oxygen evolution (OER) is crucial to enhance the practical application of zinc-air batteries. The study harnessed electrostatic forces to anchor the nanoflower-like NiCo2O4 onto graphene oxide, mitigating the poor inherent conductivity in NiCo2O4 as a transition metal oxide and preventing excessive agglomeration of the nanoflower-like structures during catalysis. Consequently, the resulting composite, NiCo2O4-GO/C, exhibited notably superior ORR and OER catalytic performance compared to pure nanoflower-like NiCo2O4. Notably, it excelled in OER catalytic activity of the OER relative to the precious metal RuO2. As a bifunctional catalyst for ORR and OER, NiCo2O4-GO/C displayed a potential difference of 0.88 V between the ORR half-wave potential and the OER potential at 10 mA·cm-2, significantly lower than the 1.08 V observed for pure flower-like NiCo2O4 and comparable to the 0.88 V exhibited by precious metal catalysts Pt/C + RuO2. The NiCo2O4-GO/C-based zinc-air battery demonstrated a discharge capacity of 817.3 mA h·g-1, surpassing that of precious metal-based zinc-air batteries. Moreover, charge-discharge cycling tests indicated the superior stability of the NiCo2O4-GO/C-based zinc-air battery compared to its precious metal-based counterparts.

Dual Active Sites of Oversaturated Fe-N5 and Fe2 O3 Nanoparticles for Accelerating Redox Kinetics of Polysulfides.

The shuttling effect and sluggish reaction kinetics are the main bottlenecks for the commercial viability of lithium-sulfur (Li-S) batteries. Metal-nitrogen-carbon single atom catalysts have attracted much attention to overcoming these obstacles due to their novel electrocatalytic activity. Herein, a novel cooperative catalytic interface with dual active sites (oversaturated Fe-N5 and polar Fe2 O3 nanocrystals) are co-embedded in nitrogen-doped hollow carbon spheres (Fe2 O3 /Fe-SA@NC) is designed by fine atomic regulation mechanism. Both experimental verifications and theoretical calculations disclose that the dual active sites (Fe-N5 and Fe2 O3 ) in this catalyst (Fe2 O3 /Fe-SA@NC) tend to form "FeS" and "LiN/O" bond, synchronically enhancing chemical adsorption and interface conversion ability of polysulfides, respectively. Specially, the Fe-N5 coordination with 3D configuration and sulfiphilic superfine Fe2 O3 nanocrystals exhibit the strong adsorption ability to facilitate the subsequent conversion reaction at dual-sites. Meanwhile, the nitrogen-doped hollow carbon spheres can promote Li+ /electron transfer and physically suppress polysulfides shuttling. Consequently, Li-S battery with the Fe2 O3 /Fe-SA@NC-modified separator exhibits a high capacity retention of 78% after 800 cycles at 1 C (pure S cathode, S content: 70 wt.%). Furthermore, the pouch cell with this separator shows good performance at 0.1 C for practical application (S loading: 4 mg cm-2 ).

Integrating a Ferroelectric Interface with a Well-Tuned Electronic Structure in Lithium-Rich Layered Oxide Cathodes for Enhanced Lithium Storage.

Li-rich layered oxides (LLOs) are considered promising candidates for new high-energy-density cathode materials for next-generation power batteries. However, their large-scale applications are largely hindered by irreversible Li/O loss, structural degradation, and interfacial side reactions during cycling. Herein, we demonstrate an integration strategy that tunes the electronic structure by La/Al codoping and constructs a ferroelectric interface on the LLOs surface through Bi0.5Na0.5TiO3 (BNT) coating. Experimental characterization reveals that the synergistic effect of the ferroelectric interface and the well-tuned electronic structure can not only promote the diffusion of Li+ and hinder the migration of On- but also suppress the lattice volume changes and reduce interfacial side reactions at high voltages up to 4.9 V vs Li+/Li. As a result, the modified material shows enhanced initial capacities and retention rates of 224.4 mAh g-1 and 78.57% after 500 cycles at 2.0-4.65 V and 231.7 mAh g-1 and 85.76% after 200 cycles at 2.0-4.9 V at 1C, respectively.

Theranostic applications of selenium nanomedicines against lung cancer.

The incidence and mortality rates of lung cancer are among the highest in the world. Traditional treatment methods include surgery, chemotherapy, and radiotherapy. Although rapid progress has been achieved in the past decade, treatment limitations remain. It is therefore imperative to identify safer and more effective therapeutic methods, and research is currently being conducted to identify more efficient and less harmful drugs. In recent years, the discovery of antitumor drugs based on the essential trace element selenium (Se) has provided good prospects for lung cancer treatments. In particular, compared to inorganic Se (Inorg-Se) and organic Se (Org-Se), Se nanomedicine (Se nanoparticles; SeNPs) shows much higher bioavailability and antioxidant activity and lower toxicity. SeNPs can also be used as a drug delivery carrier to better regulate protein and DNA biosynthesis and protein kinase C activity, thus playing a role in inhibiting cancer cell proliferation. SeNPs can also effectively activate antigen-presenting cells to stimulate cell immunity, exert regulatory effects on innate and regulatory immunity, and enhance lung cancer immunotherapy. This review summarizes the application of Se-based species and materials in lung cancer diagnosis, including fluorescence, MR, CT, photoacoustic imaging and other diagnostic methods, as well as treatments, including direct killing, radiosensitization, chemotherapeutic sensitization, photothermodynamics, and enhanced immunotherapy. In addition, the application prospects and challenges of Se-based drugs in lung cancer are examined, as well as their forecasted future clinical applications and sustainable development.

Reactive Polymer as Artificial Solid Electrolyte Interface for Stable Lithium Metal Batteries.

Lithium (Li) metal anodes have the highest theoretical capacity and lowest electrochemical potential making them ideal for Li metal batteries (LMBs). However, Li dendrite formation on the anode impedes the proper discharge capacity and practical cycle life of LMBs, particularly in carbonate electrolytes. Herein, we developed a reactive alternative polymer named P(St-MaI) containing carboxylic acid and cyclic ether moieties which would in situ form artificial polymeric solid electrolyte interface (SEI) with Li. This SEI can accommodate volume changes and maintain good interfacial contact. The presence of carboxylic acid and cyclic ether pendant groups greatly contribute to the induction of uniform Li ion deposition. In addition, the presence of benzyl rings makes the polymer have a certain mechanical strength and plays a key role in inhibiting the growth of Li dendrites. As a result, the symmetric Li||Li cell with P(St-MaI)@Li layer can stably cycle for over 900 h under 1 mA cm-2 without polarization voltage increasing, while their Li||LiFePO4 full batteries maintain high capacity retention of 96 % after 930 cycles at 1C in carbonate electrolytes. The innovative strategy of artificial SEI is broadly applicable in designing new materials to inhibit Li dendrite growth on Li metal anodes.

[Germplasm resource evaluation of Chrysanthemi Indici Flos based on color and chemical components].

This study explored the correlation between color and chemical components of Chrysanthemi Indici Flos(CIF), aiming at providing a reference for its procurement, evaluation, and breeding. Colorimeter and ultra-performance liquid chromatograph(UPLC) were used to determine the color(lightness-shade chromaticity value L~*, red-green chromaticity value a~*, yellow-blue chromati-city value b~*) and chemical components(cynaroside, linarin, luteolin, apigenin, and chlorogenic acid) of 84 CIF germplasms, respectively. Diversity analysis, correlation analysis, regression analysis, and cluster analysis were performed. The results showed that the color and chemical components of CIF were diversified. Chlorogenic acid was in significantly positive correlation with L~* and b~* and significantly negative correlation with a~*. Cynaroside and grey relational grade γ_i of chemical components were in significantly po-sitive correlation with b~* and L~*, respectively, whereas linarin, luteolin, and apigenin had no significant correlation with L~*, a~*, or b~*. The 84 CIF germplasms were clustered into 4 clades. In addition, germplasms in clade Ⅲ had higher γ_i and total color value(E~*_(ab)) than those in other clades, with the best quality and color, and a germplasm with the highest quality, bright yellow color, and highest content of linarin was screened out in this clade. Thus, CIF with bright yellow color had high content of cymaroside and chlorogenic acid and thereby high quality. In summary, the color can be used to quickly predict the quality of CIF. Our results provided data for the evaluation of CIF quality by color and a reference for its procurement and breeding.

2D Titania-Carbon Superlattices Vertically Encapsulated in 3D Hollow Carbon Nanospheres Embedded with 0D TiO2 Quantum Dots for Exceptional Sodium-Ion Storage.

Two-dimensional (2D) superlattices offer promising technological opportunities in tuning the intercalation chemistry of metal ions. Now, well-ordered 2D superlattices of monolayer titania and carbon with tunable interlayer-spacing are synthesized by a molecularly mediated thermally induced approach. The 2D superlattices are vertically encapsulated in hollow carbon nanospheres, which are embedded with TiO2 quantum dots, forming a 0D-2D-3D multi-dimensional architecture. The multi-dimensional architecture with the 2D superlattices encapsulated inside exhibits a near zero-strain characteristic and enriched electrochemical reactivity, achieving a highly efficient Na+ storage performance with exceptional rate capability and superior long-term cyclability.

Improving the Electrochemical Properties of the Manganese-Based P3 Phase by Multiphasic Intergrowth.

Layered transition-metal oxides are one kind of the most promising cathode materials for sodium-ion batteries. In this study, we propose a strategy to enhance the electrochemical properties of P3-type manganese-based layered oxide cathode by introducing a small amount of layered P2 and Li-O'3 phases. Powder X-ray diffraction (PXRD) structural refinement and aberration-corrected scanning transmission electron microscopy (STEM) are performed to confirm the microstructures of different samples. PXRD refinement results show that the elevated annealing temperature leads to a partial conversion of the P3 phase to the P2 phase and the addition of lithium results in the formation of a new O'3 phase in the P3/P2-layered matrix. STEM results identify the intergrowth of P3/P2 and P3/P2/O'3 in biphasic and triphasic materials, respectively. Electron energy loss spectroscopy verifies that the alkali metal layer in the O'3 phase is occupied by the lithium ion. The intergrowth of biphasic and triphasic materials in these layered P3/P2 and P3/P2/O'3 hybrid structures brings forth a positive effect on the electrochemical properties. In particular, the formation of P3/P2/O'3-intergrown hybrid structures greatly improves the cycling stability of the P3 phase that the capacity retention of P3/P2/O'3 hybrid structures remains 78%, while capacity retention of the pure P3 phase is only 54.1% after 50 cycles at a rate of 0.2 C, and the rate performance of the P3 phase has also been enhanced.

Understanding the Improved Kinetics and Cyclability of a Li2MnSiO4 Cathode with Calcium Substitution.

Limited practical capacity and poor cyclability caused by sluggish kinetics and structural instability are essential aspects that constrain the potential application of Li2MnSiO4 cathode materials. Herein, Li2Mn1- xCa xSiO4/C nanoplates are synthesized using a diethylene-glycol-assisted solvothermal method, targeting to circumvent its drawbacks. Compared with the pristine material, the Ca-substituted material exhibits enhanced electrochemical kinetics and improved cycle life performance. In combination with experimental studies and first-principles calculations, we reveal that Ca incorporation enhances electronic conductivity and the Li-ion diffusion coefficient of the Ca-substituted material, and it improves the structural stability by reducing the lattice distortion. It also shrinks the crystal size and alleviates structure collapse to enhance cycling performance. It is demonstrated that Ca can alleviate the two detrimental factors and shed lights on the further searching for suitable dopants.

Component-Customizable Porous Rare-Earth-Based Colloidal Spheres towards Highly Effective Catalysts and Bioimaging Applications.

Multicomponent porous colloidal spheres are of interest because they not only show a combination of the properties associated with all different components, but also usually present synergy effects. However, a combination of different components in a single porous sphere is still greatly challenged due to the different precipitation behaviors of each component. In this work, we have developed a general synthetic route to prepare several categories of porous monodisperse rare-earth (RE)-based colloidal spheres with customizable elemental compositions and a uniform element distribution. The two-step synthetic strategy is based on the integration of coordination chemistry precipitation of RE ions and a subsequent ion-exchange process, which steers clear of obstacles, such as differences in solubility product constant, that are to be found in traditional co-precipitation methods. Our approach provides a new mixing mechanism to realize homogeneous distribution of each element within the porous spheres. An array of binary, ternary, and even senary RE colloidal porous spheres with diameters of 500 nm to 700 nm has been successfully synthesized. Taking advantage of their good dispersibility, porosity, and customizable components, these porous RE oxide spheres show excellent catalytic activity for the reduction of 4-nitrophenol, and promising application in single-phase multifunctional bioprobes.

Design and evaluation of potentiometric principles for bladder volume monitoring: a preliminary study.

Recent advances in microelectronics and wireless transmission technology have led to the development of various implantable sensors for real-time monitoring of bladder conditions. Although various sensing approaches for monitoring bladder conditions were reported, most such sensors have remained at the laboratory stage due to the existence of vital drawbacks. In the present study, we explored a new concept for monitoring the bladder capacity on the basis of potentiometric principles. A prototype of a potentiometer module was designed and fabricated and integrated with a commercial wireless transmission module and power unit. A series of in vitro pig bladder experiments was conducted to determine the best design parameters for implementing the prototype potentiometric device and to prove its feasibility. We successfully implemented the potentiometric module in a pig bladder model in vitro, and the error of the accuracy of bladder volume detection was <±3%. Although the proposed potentiometric device was built using a commercial wireless module, the design principles and animal experience gathered from this research can serve as a basis for developing new implantable bladder sensors in the future.

Entropy-Driven Hybrid Gel Electrolyte Enables Practical High-Voltage Lithium Metal Batteries.

Electrolyte engineering plays a crucial role in enhancing the performance of lithium metal batteries (LMBs) featuring high-voltage cathodes and limited lithium anodes, thereby unlocking their potential for high-energy electrochemical storage. Herein, an entropy-driven hybrid gel electrolyte with enhanced diversity in Li-ion solvation structures is designed by incorporating substantial amounts of insoluble LiPO2F2 and LiNO3 salts into LiPF6-based carbonate electrolytes, followed by in situ thermal polymerization. Specifically, the Li+ solvation structures are modulated via ionophilic NO3- and PO2F2- to generate an anion-rich solvation sheath and thus promote anion reduction at the electrode-electrolyte interface. The interfaces enriched in anion-derived inorganic components facilitate rapid ionic transport, thus enabling smooth and dense Li morphology and ultimately enhancing the electrochemical performance of LMBs. As a result, this high-hybrid gel electrolyte confers LMBs employing high-voltage NCM cathodes, as demonstrated by sustained performance in both coin-cell (500 cycles at 4.5 V) and Ah-level pouch cell configurations under practical conditions (60 cycles, N/P: 1.92, and E/C: 2.0 g Ah -1).

Diagnostic procedure for localized constrictive pericarditis leading to bilateral pleural effusion: two case reports.

Constrictive pericarditis is a rare disease. Localized constrictive pericarditis leading to bilateral pleural effusion is more difficult to recognize, and the diagnostic procedure can be ambiguous. Here, we report two patients diagnosed with localized constrictive pericarditis who presented with bilateral pleural effusion. A thorough work-up showed that the pleural effusion was nonspecific, as was the pathology of the pleura. One patient had a history of pericardial effusion 2 years ago, and the other had undergone surgery for an anterior mediastinum teratoma. Pericardial scarring was found on their chest CT scans. The patients underwent pericardiectomy, and localized pericardial thickening was excised. The bilateral pleural effusion was effectively cured, and the patients showed satisfactory recovery on follow-up. Physicians should be aware of localized pericarditis leading to bilateral pleural effusion, and pericardiectomy is an effective diagnostic and therapeutic procedure.

Crosslinked solubilizer enables nitrate-enriched carbonate polymer electrolytes for stable, high-voltage lithium metal batteries.

High-voltage lithium metal batteries (LMBs) have been considered promising next-generation high-energy-density batteries. However, commercial carbonate electrolytes can scarcely be employed in LMBs owing to their poor compatibility with metallic lithium. N,N-dimethylacrylamide (DMAA)-a crosslinkable solubilizer with a high Gutmann donor number-is employed to facilitate the dissolution of insoluble lithium nitrate (LiNO3) in carbonate-based electrolytes and to form gel polymer electrolytes (GPEs) through in situ polymerization. The Li+ solvation structure of the GPEs is regulated using LiNO3 and DMAA, which suppresses the decomposition of LiPF6 and facilitates the formation of an inorganic-rich solid electrolyte interface. Consequently, the Coulombic efficiency (CE) of the Li||Cu cell assembled with a GPE increases to 98.5% at room temperature, and the high-voltage Li||NCM622 cell achieves a capacity retention of 80.1% with a high CE of 99.5% after 400 cycles. The bifunctional polymer electrolytes are anticipated to pave the way for next-generation high-voltage LMBs.

Molten-Salt-Assisted Strategy Enables High-Rate Micron-Sized Single-Crystal Li-Rich, Mn-Based Layered Oxide Cathode Materials.

Li-rich Mn-based layered oxides (LMLOs) are expected to be the most promising high-capacity cathodes for the next generation of lithium-ion batteries (LIBs). However, the poor cycling stability and kinetics performance of polycrystalline LMLOs restrict their practical applications due to the anisotropic lattice stress and crack propagation during cycling. Herein, B-doped micron-sized single-crystal Co-free LMLOs were obtained by molten-salt (LiNO3 and H3BO3)-assisted sintering. The results reveal that the low-melting-point molten salt can serve as liquid-phase media to improve the efficiency of atomic mass transfer and crystal nucleation and growth. The modified single-crystal LMLO cathodes can resist the accumulation of anisotropic stress and strain during the cycling and reduce interface side reactions, thus achieving excellent high-voltage stability and kinetics performance. The reversible specific capacity of the single crystals is 210.8 mAh g-1 at 1C with a voltage decay rate of 1.95 mV/cycle and up to 161.1 mAh g-1 at 10C with a capacity retention of 81.06% after 200 cycles.

Orderly Arranged Dipoles Regulate Anion-Derived Solid-Electrolyte Interphase for Stable Lithium Metal Chemistry.

Lithium (Li) metal batteries are considered the most promising high-energy-density electrochemical energy storage devices of the next generation. However, the unstable solid-electrolyte interphase (SEI) derived from electrolytes usually leads to high impedance, Li dendrites growth, and poor cyclability. Herein, the ferroelectric BaTiO3 with orderly arranged dipoles (BTOV) is integrated into the polypropylene separator as a functional layer. Detailed characterizations and theoretical calculations indicate that surface oxygen vacancies drive the phase transition of BaTiO3 materials and promote the ordered arrangement of dipoles. The strong dipole moments in BTOV can adsorb TFSI- and NO3 - anions selectively and promote their preferential reduction to form a SEI film enriched with inorganic LiF and LiNxOy species, thus facilitating the rapid transfer of Li+ and restraining the growth of Li dendrites. As a result, the Li-Li cell with the BTOV functional layer exhibits enhanced Li plating/stripping cycling with an ultra-long life of over 7000 h at 0.5 mA cm-2/1.0 mAh cm-2. The LiFePO4 || Li (50 µm) full cells display excellent cycling performance exceeding 1760 cycles and superior rate performance. This work provides a new perspective for regulating SEI chemistry by introducing ordered dipoles to control the distribution and reaction of anions.

Organoboron- and Cyano-Grafted Solid Polymer Electrolytes Boost the Cyclability and Safety of High-Voltage Lithium Metal Batteries.

Solid-state polymer electrolytes (SPEs) are deemed as a class of sought-after candidates for high-safety and high-energy-density solid-state lithium metal batteries, but their low ionic conductivity, narrow electrochemical windows, and severe interfacial deterioration limit their practical implementations. Herein, an organoboron- and cyano-grafted polymer electrolyte (PVNB) was designed using vinylene carbonate as the polymer backbone and organoboron-modified poly(ethylene glycol) methacrylate and acrylonitrile as the grafted phases, which may facilitate Li-ion transport, immobilize the anions, and enlarge the oxidation voltage window; therefore, the well-tailored PVNB exhibits a high Li-ion transference number (tLi+ = 0.86), a wide electrochemical window (>5 V), and a high ionic conductivity (σ = 9.24 × 10-4 S cm-1) at room temperature (RT). As a result, the electrochemical cyclability and safety of the Li|LiFePO4 and Li|LiNi0.8Co0.1Mn0.1O2 cells with in situ polymerization of PVNB are substantially improved by forming the stable organic-inorganic composite cathode electrolyte interphase (CEI) and the Li3N-LiF-rich solid electrolyte interphase (SEI).

In Situ Formed Heterostructure Interface and Well-Tuned Electronic Structure Ensuring Long Cycle Stability for 4.9 V High-Voltage Li-Rich Layered Oxide Cathodes.

High-voltage lithium-rich manganese-based layered oxides (LMLOs) are considered as the most competitive cathode materials for next-generation high-energy-density lithium-ion batteries (LIBs). However, LMLOs still suffer from irreversible lattice oxygen release, uncontrollable interface side reactions, and surface structural degradation. Herein, we propose an integration strategy combining La/Al codoping and LixCoPO4 nanocoating to improve the electrochemical performance of LMLOs comprehensively. La/Al codoping regulates the electronic structure to enhance the redox activity of anions and cations and inhibit structural degradation. The LixCoPO4 nanocoating formed by in situ reaction with the surface residual lithium can not only promote Li-ion migration but also reduce interfacial side reactions. The induced Layered@Rocksalt@LixCoPO4 heterostructure suppresses lattice volume variation and structural degradation during cycling. Under the synergistic effect of the heterostructure interface and well-tuned electronic structure, the capacity retention rate of comodified LMLO materials reaches 80.06% after 500 cycles (2.0-4.65 V) and 75.1% after 340 cycles at 1C under a high cut-off voltage of 4.9 V.

Evaluation of Chrysanthemi Indici Flos germplasms based on nine bioactive constituents and color parameters.

Chrysanthemi Indici Flos (CIF) is the inflorescence of Chrysanthemum indicum L., which exists in various shades of yellow and has pharmacologically active constituents. It is widely used for medicinal purposes in China, Japan, and South Korea to treat inflammatory diseases. Its external color is usually used to judge its internal quality in trade; however, the correlation between its color and chemical constituents is unknown. Here, we simultaneously determined five phenylpropanoids (neochlorogenic acid, chlorogenic acid, and isochlorogenic acids A, B, and C) and four flavonoids (linarin, luteolin, apigenin, and acacetin) of 70 CIF germplasms using a newly established UPLC method; furthermore, we measured their color parameters (L*, a*, and b*) using a spectrophotometer. Our results showed considerable variations in the bioactive constituent contents and color parameters of CIF. The content of the five phenylpropanoids and the relative correlation degree γi of the nine constituents were positively correlated with color parameters, which could be rapidly predicted based on L* and/or b*. Moreover, we screened out a high-quality germplasm with a high linarin content and bright colors using the hierarchical clustering method. Our results provide comprehensive insight into CIF's quality evaluation process, particularly the methods for procuring high-quality medicinal materials and breeding by color.