"Water-in-Salt" Electrolyte Suppressed MnVOPO4·2H2O Cathode Dissolution for Stable High-Voltage Platform and Cycling Performance for Aqueous Zinc Metal Battery.

Vanadium-based materials have the advantages of abundant valence states and stable structures, having great application potential as cathode materials in metal-ion batteries. However, their low voltage and vanadium dissolution in traditional water-based electrolytes greatly limit their application and development in aqueous zinc metal batteries (AZMBs). Herein, phosphate- and vanadium-based cathode materials (MnVOPO4·2H2O) with stacked layers and few defects were prepared via a condensation reflux method and then combined with a high-concentration electrolyte (21 m LiTFSI + 1 M Zn(CF3SO3)2) to address these limitations. The specific capacity and cycle stability accompanying the stable high voltage of 1.39 V were significantly enhanced compared with those for the traditional electrolyte of 3 M Zn(CF3SO3)2, benefiting from the suppressed vanadium dissolution. The cathode materials of MnVOPO4·2H2O achieved a high specific capacity of 152 mAh g-1 at 0.2 A g-1, with a retention rate of 86% after 100 cycles for AZMBs. A high energy density of 211.78 Wh kg-1 was also achieved. This strategy could illuminate the significance of electrolyte modification and provide potential high-voltage cathode materials for AZMBs and other rechargeable batteries.

Strategically Modulating Proton Activity and Electric Double Layer Adsorption for Innovative All-Vanadium Aqueous Mn2+/Proton Hybrid Batteries.

Aqueous Mn-ion batteries (MIBs) exhibit a promising development potential due to their cost-effectiveness, high safety, and potential for high energy density. However, the development of MIBs is hindered by the lack of electrode materials capable of storing Mn2+ ions due to acidic manganese salt electrolytes and large ion radius. Herein, the tunnel-type structure of monoclinic VO2 nanorods to effectively store Mn2+ ions via a reversible (de)insertion chemistry for the first time is reported. Utilizing exhaustive in situ/ex situ multi-scale characterization techniques and theoretical calculations, the co-insertion process of Mn2+/proton is revealed, elucidating the capacity decay mechanism wherein high proton activity leads to irreversible dissolution loss of vanadium species. Further, the Grotthuss transfer mechanism of protons is broken via a hydrogen bond reconstruction strategy while achieving the modulation of the electric double-layer structure, which effectively suppresses the electrode interface proton activity. Consequently, the VO2 demonstrates excellent electrochemical performance at both ambient temperatures and -20 °C, especially maintaining a high capacity of 162 mAh g-1 at 5 A g-1 after a record-breaking 20 000 cycles. Notably, the all-vanadium symmetric pouch cells are successfully assembled for the first time based on the "rocking-chair" Mn2+/proton hybrid mechanism, demonstrating the practical application potential.

Twin Embryos in Arabidopsis thaliana KATANIN 1 Mutants.

Regulation of microtubule dynamics is crucial during key developmental transitions such as gametogenesis, fertilization, embryogenesis, and seed formation, where cells undergo rapid changes in shape and function. In plants, katanin plays an essential role in microtubule dynamics. This study investigates two seed developmental mutants in Arabidopsis thaliana, named elk5-1D (erecta-like 5, ELK5) and loo1 (lollipop 1), which are characterized by round seeds, dwarfism, and fertility defects. Notably, elk5-1D exhibits a dominant inheritance pattern, whereas loo1 is recessive. Through positional cloning, we identified both mutants as new alleles of the KATANIN 1 (KTN1) gene, which encodes a microtubule-severing enzyme critical for cell division and morphology. Mutations in KTN1 disrupt embryo cell division and lead to the emergence of a twin embryo phenotype. Our findings underscore the essential role of KTN1 in fertility and early embryonic development, potentially influencing the fate of reproductive cells.

Two imprinted genes primed by DEMETER in the central cell and activated by WRKY10 in the endosperm.

The early development of the endosperm is crucial for balancing the allocation of maternal nutrients to offspring. This process is believed to be evolutionarily associated with genomic imprinting, resulting in parentally biased allelic gene expression. Beyond FertilizationIndependentSeed (FIS) genes, the number of imprinted genes involved in early endosperm development and seed size determination remains limited. This study introduces early endosperm-expressed HAIKU (IKU) downstream Candidate F-box 1 (ICF1) and ICF2 as maternally expressed imprinted genes (MEGs) in Arabidopsis thaliana. Although these genes are also demethylated by DEMETER (DME) in the central cell, their activation differs from the direct DME-mediated activation seen in classical MEGs such as the FIS genes. Instead, ICF maternal alleles carry pre-established hypomethylation in their promoters, priming them for activation by the WRKY10 transcription factor in the endosperm. On the contrary, paternal alleles are predominantly suppressed by CG methylation. Furthermore, we find that ICF genes partially contribute to the small seed size observed in iku mutants. Our discovery reveals a two-step regulatory mechanism that highlights the important role of conventional transcription factors in the activation of imprinted genes, which was previously not fully recognized. Therefore, the mechanism provides a new dimension to understand the transcriptional regulation of imprinting in plant reproduction and development.

Short-Chain Sulfur Confined into Nitrogen-Doped Hollow Carbon Nanospheres for High-Capacity Potassium Storage.

Carbon-based materials are one of the ideal negative electrode materials for potassium ion batteries. However, the limited active sites and sluggish diffusion ion kinetics still hinder its commercialization process. To address these problems, we design a novel carbon composite anode, by confining highly reactive short-chain sulfur molecules into nitrogen-doped hollow carbon nanospheres (termed SHC-450). The formation process involves the controlled synthesis of hollow polyaniline (PANI) nanospheres as precursors via an Ostwald ripening mechanism and subsequent sulfuration treatment. The high content of constrained short-chain sulfur molecules (20.94 wt%) and considerable N (7.15 wt%) ensure sufficient active sites for K+ storage in SHC-450. Accordingly, the SHC-450 electrode exhibits a high reversible capacity of 472.05 mAh g-1 at 0.1 A g-1 and good rate capability (172 mAh g-1 at 2 A g-1). Thermogravimetric analysis shows that SHC-450 has impressive thermal stability to withstand a high temperature of up to 640 °C. Ex situ spectroscopic characterizations reveal that the short-chain sulfur provides high capacity through reversible formation of K2S. Moreover, its special hollow structure not only provides ample space for highly active short-chain sulfur reactants but also effectively mitigates volume expansion during the sulfur conversion process. This work offers new perspectives on enhanced K+ storage performance from an interesting anode design and the space-limited domain principle.

Co/Al Co-Substituted Layered Manganese-Based Oxide Cathode for Stable and High-Rate Potassium-Ion Batteries.

Manganese-based layered oxides are promising cathode materials for potassium-ion batteries (PIBs) due to their low cost and high theoretical energy density. However, the Jahn-Teller effect of Mn3+ and sluggish diffusion kinetics lead to rapid electrode deterioration and a poor rate performance, greatly limiting their practical application. Here, we report a Co/Al co-substitution strategy to construct a P3-type K0.45Mn0.7Co0.2Al0.1O2 cathode material, where Co3+ and Al3+ ions occupy Mn3+ sites. This effectively suppresses the Jahn-Teller distortion and alleviates the severe phase transition during K+ intercalation/de-intercalation processes. In addition, the Co element contributes to K+ diffusion, while Al stabilizes the layer structure through strong Al-O bonds. As a result, the K0.45Mn0.7Co0.2Al0.1O2 cathode exhibits high capacities of 111 mAh g-1 and 81 mAh g-1 at 0.05 A g-1 and 1 A g-1, respectively. It also demonstrates a capacity retention of 71.6% after 500 cycles at 1 A g-1. Compared to the pristine K0.45MnO2, the K0.45Mn0.7Co0.2Al0.1O2 significantly alleviates severe phase transition, providing a more stable and effective pathway for K+ transport, as investigated by in situ X-ray diffraction. The synergistic effect of Co/Al co-substitution significantly enhances the structural stability and electrochemical performance, contributing to the development of new Mn-based cathode materials for PIBs.

Progress on Transition Metal Ions Dissolution Suppression Strategies in Prussian Blue Analogs for Aqueous Sodium-/Potassium-Ion Batteries.

Aqueous sodium-ion batteries (ASIBs) and aqueous potassium-ion batteries (APIBs) present significant potential for large-scale energy storage due to their cost-effectiveness, safety, and environmental compatibility. Nonetheless, the intricate energy storage mechanisms in aqueous electrolytes place stringent requirements on the host materials. Prussian blue analogs (PBAs), with their open three-dimensional framework and facile synthesis, stand out as leading candidates for aqueous energy storage. However, PBAs possess a swift capacity fade and limited cycle longevity, for their structural integrity is compromised by the pronounced dissolution of transition metal (TM) ions in the aqueous milieu. This manuscript provides an exhaustive review of the recent advancements concerning PBAs in ASIBs and APIBs. The dissolution mechanisms of TM ions in PBAs, informed by their structural attributes and redox processes, are thoroughly examined. Moreover, this study delves into innovative design tactics to alleviate the dissolution issue of TM ions. In conclusion, the paper consolidates various strategies for suppressing the dissolution of TM ions in PBAs and posits avenues for prospective exploration of high-safety aqueous sodium-/potassium-ion batteries.

Sulfurized polyacrylonitrile as cathodes for advanced lithium-sulfur batteries: advances in modification strategies.

Sulfurized polyacrylonitrile (S@PAN) composites have gathered a lot of interest because of their advantages of high theoretical energy density, excellent cycling stability, and environmental friendliness. Meanwhile, their unique "covalent bonding" mechanism effectively avoids the dissolution and shuttling of polysulfides, and thus they are expected to be the most promising candidate for the cathode material in lithium-sulfur (Li-S) batteries. Over the past five years, S@PAN cathode materials have been widely studied in Li-S batteries, and it is very important to summarize the advances over time for their practical applications. This article reviews the latest progress concerning the modification of S@PAN cathode materials for improving poor electrical conductivity, low sulfur content, and sluggish reaction kinetics, and proposes possible research directions. We hope this review provides valuable insights and references for future research on Li-S batteries.

Comprehensive Understandings of Hydrogen Bond Chemistry in Aqueous Batteries.

Aqueous batteries are emerging as highly promising contenders for large-scale grid energy storage because of uncomplicated assembly, exceptional safety, and cost-effectiveness. The unique aqueous electrolyte with a rich hydrogen bond (HB) environment inevitably has a significant impact on the electrode materials and electrochemical processes. While numerous reviews have focused on the materials design and assembly of aqueous batteries, the utilization of HB chemistry is overlooked. Herein, instead of merely compiling recent advancements, this review presents a comprehensive summary and analysis of the profound implication exerted by HB on all components of the aqueous batteries. Intricate links between the novel HB chemistry and various aqueous batteries are ingeniously constructed within the critical aspects, such as self-discharge, structural stability of electrode materials, pulverization, solvation structures, charge carrier diffusion, corrosion reactions, pH sensitivity, water splitting, polysulfides shuttle, and H2 S evolution. By adopting a vantage point that encompasses material design, binder and separator functionalization, electrolyte regulation, and HB optimization, a critical examination of the key factors that impede electrochemical performance in diverse aqueous batteries is conducted. Finally, insights are rendered properly based on HB chemistry, with the aim of propelling the advancement of state-of-the-art aqueous batteries.

Proton/Mg2+ Co-Insertion Chemistry in Aqueous Mg-Ion Batteries: From the Interface to the Inner.

Co-insertion of protons happens widely and enables divalent-ion aqueous batteries to achieve high performances. However, detailed investigations and comprehensive understandings of proton co-insertion are scarce. Herein, we demonstrate that proton co-insertion into tunnel materials is determined jointly by interface derivation and inner diffusion: at the interface, hdrated Mg2+ has poor insertion kinetics, and therefore accumulates and hydrolyzes to produce protons; in the tunnels, co-inserted/lattice H2 O molecules block the Mg2+ diffusion while facilitate the proton diffusion. When monoclinic vanadium dioxide (VO2 (B)) anode is tested in Mg(CH3 COO)2 aqueous solution, the formation of Mg-rich solid electrolyte interphase on the VO2 (B) electrode and co-insertion of derived protons are probed; in the tunnels, the diffusion energy barrier of Mg2+ +H2 O is 2.7 eV, while that of the protons is 0.37 eV. Thus, protons dominate the subsequent insertion and inner diffusion. As a consequence, the VO2 (B) achieves a high capacity of 257.0 mAh g-1 at 1 A g-1 , a high rate retention of 59.1 % from 1 to 8 A g-1 , and stable cyclability of 3000 times with a capacity retention of 81.5 %. This work provides an in-depth understanding of the proton co-insertion and may promote the development of rechargeable aqueous batteries.

Hierarchical Carbon Network Composites Derived from ZIF-8 for High-Efficiency Microwave Absorption.

Metal-organic framework (MOF)-derived composites have gained wide attention due to their specific structures and enhanced performance. In this work, we prepared carbon nanotubes with Fe nanoparticles connected to two-dimensional (2D) hierarchical carbon network composites via a low-pressure gas-solid reaction strategy. Specifically, the three-dimensional (3D) networks derived from ZIF-8 exploited the carbon nanotubes with the function of charge modulation. Meanwhile, we utilized the interconnected 2D nanostructures to optimize impedance matching and facilitate multiple scattering, ultimately improving the overall microwave absorption performance. Furthermore, based on the well-designed structures, the composites prepared at 800 °C (Fe-N-C@CNTs-800) achieved the best reflection loss (RL) of -58.5 dB, thereby obtaining superior microwave absorption performance. Overall, this study provides a good groundwork for further investigation into the modification and dimension design of novel hierarchical microwave absorbers.

Highly Crystalline Prussian Blue for Kinetics Enhanced Potassium Storage.

Prussian blue analogs (PBAs) are promising cathode materials for potassium-ion batteries (KIBs) owing to their large open framework structure. As the K+ migration rate and storage sites rely highly on the periodic lattice arrangement, it is rather important to guarantee the high crystallinity of PBAs. Herein, highly crystalline K2 Fe[Fe(CN)6 ] (KFeHCF-E) is synthesized by coprecipitation, adopting the ethylenediaminetetraacetic acid dipotassium salt as a chelating agent. As a result, an excellent rate capability and ultra-long lifespan (5000 cycles at 100 mA g-1 with 61.3% capacity maintenance) are achieved when tested in KIBs. The highest K+ migration rate of 10-9 cm2 s-1 in the bulk phase is determined by the galvanostatic intermittent titration technique. Remarkably, the robust lattice structure and reversible solid-phase K+ storage mechanism of KFeHCF-E are proved by in situ XRD. This work offers a simple crystallinity optimization method for developing high-performance PBAs cathode materials in advanced KIBs.

A High-Energy NASICON-Type Na3.2 MnTi0.8 V0.2 (PO4 )3 Cathode Material with Reversible 3.2-Electron Redox Reaction for Sodium-Ion Batteries.

Na superionic conductor (NASICON) structured cathode materials with robust structural stability and large Na+ diffusion channels have aroused great interest in sodium-ion batteries (SIBs). However, most of NASICON-type cathode materials exhibit redox reaction of no more than three electrons per formula, which strictly limits capacity and energy density. Herein, a series of NASICON-type Na3+x MnTi1-x Vx (PO4 )3 cathode materials are designed, which demonstrate not only a multi-electron reaction but also high voltage platform. With five redox couples from V5+/4+ (≈4.1 V), Mn4+/3+ (≈4.0 V), Mn3+/2+ (≈3.6 V), V4+/3+ (≈3.4 V), and Ti4+/3+ (≈2.1 V), the optimized material, Na3.2 MnTi0.8 V0.2 (PO4 )3 , realizes a reversible 3.2-electron redox reaction, enabling a high discharge capacity (172.5 mAh g-1 ) and an ultrahigh energy density (527.2 Wh kg-1 ). This work sheds light on the rational construction of NASICON-type cathode materials with multi-electron redox reaction for high-energy SIBs.

Graphite-Based Composite Anodes with C-O-Nb Heterointerfaces Enable Fast Lithium Storage.

To better satisfy the increasing demands for electric vehicles, it is crucial to develop fast-charging lithium-ion batteries (LIBs). However, the fast-charging capability of commercial graphite anodes is limited by the sluggish Li+ insertion kinetics. Herein, we report a synergistic engineering of uniform nano-sized T-Nb2 O5 particles on graphite (Gr@Nb2 O5 ) with C-O-Nb heterointerfaces, which prevents the growth and aggregation of T-Nb2 O5 nanoparticles. Through detailed theoretical calculations and pair distribution function analysis, the stable existence of the heterointerfaces is proved, which can accelerate the electron/ion transport. These heterointerfaces endow Gr@Nb2 O5 anodes with high ionic conductivity and excellent structural stability. Consequently, Gr@10-Nb2 O5 anode, where the mass ratio of T-Nb2 O5 /graphite=10/100, exhibits excellent cyclic stability and incredible rate capabilities, with 100.5 mAh g-1 after 10000 stable cycles at an ultrahigh rate of 20 C. In addition, the synergistic Li+ storage mechanism is revealed by systematic electrochemical characterizations and in situ X-ray diffraction. This work offers new insights to the reasonable design of fast-charging graphite-based anodes for the next generation of LIBs.

Advances in green solvents for production of polysaccharide-based packaging films: Insights of ionic liquids and deep eutectic solvents.

The problems with plastic materials and the good film-forming properties of polysaccharides motivated research in the development of polysaccharide-based films. In the last 5 years, there has been an explosion of publications on using green solvents, including ionic liquids (ILs), and deep eutectic solvents (DESs) as candidates to substitute the conventional solvents/plasticizers for preparations of desired polysaccharide-based films. This review summarizes related properties and recovery of ILs and DESs, a series of green preparation strategies (including pretreatment solvents/reaction media, ILs/DESs as components, extraction solvents of bioactive compounds added into films), and inherent properties of polysaccharide-based films with/without ILs and DESs. Major reported advantages of these new solvents are high dissolving capacity of certain ILs/DESs for polysaccharides (i.e., up to 30 wt% for cellulose) and better plasticizing ability than traditional plasticizers. In addition, they frequently display intrinsic antioxidant and antibacterial activities that facilitate ILs/DESs applications in the processing of polysaccharide-based films (especially active food packaging films). ILs/DESs in the film could also be further recycled by water or ethanol/methanol treatment followed by drying/evaporation. One particularly promising approach is to use bioactive cholinium-based ILs and DESs with good safety and plasticizing ability to improve the functional properties of prepared films. Whole extracts by ILs/DESs from various byproducts can also be directly used in films without separation/polishing of compounds from the extracting agents. Scaling-up, including costs and environmental footprint, as well as the safety and applications in real foods of polysaccharide-based film with ILs/DESs (extracts) deserves more studies.

Comprehensive H2 O Molecules Regulation via Deep Eutectic Solvents for Ultra-Stable Zinc Metal Anode.

The corrosion, parasitic reactions, and aggravated dendrite growth severely restrict development of aqueous Zn metal batteries. Here, we report a novel strategy to break the hydrogen bond network between water molecules and construct the Zn(TFSI)2 -sulfolane-H2 O deep eutectic solvents. This strategy cuts off the transfer of protons/hydroxides and inhibits the activity of H2 O, as reflected in a much lower freezing point (<-80 °C), a significantly larger electrochemical stable window (>3 V), and suppressed evaporative water from electrolytes. Stable Zn plating/stripping for over 9600 h was obtained. Based on experimental characterizations and theoretical simulations, it has been proved that sulfolane can effectively regulate solvation shell and simultaneously build the multifunctional Zn-electrolyte interface. Moreover, the multi-layer homemade modular cell and 1.32 Ah pouch cell further confirm its prospect for practical application.

Dietary Polyphenols as Prospective Natural-Compound Depression Treatment from the Perspective of Intestinal Microbiota Regulation.

The broad beneficial effects of dietary polyphenols on human health have been confirmed. Current studies have shown that dietary polyphenols are important for maintaining the homeostasis of the intestinal microenvironment. Moreover, the corresponding metabolites of dietary polyphenols can effectively regulate intestinal micro-ecology and promote human health. Although the pathogenesis of depression has not been fully studied, it has been demonstrated that dysfunction of the microbiota-gut-brain axis may be its main pathological basis. This review discusses the interaction between dietary polyphenols and intestinal microbiota to allow us to better assess the potential preventive effects of dietary polyphenols on depression by modulating the host gut microbiota.

Towards a Stable Layered Vanadium Oxide Cathode for High-Capacity Calcium Batteries.

Calcium-based batteries have promising advantages over multivalent ion batteries. However, the fabrication of highly efficient calcium batteries is limited by the quality of available cathode materials, which motivates the exploration of electrodes that can enable reversible, stable Ca2+ intercalation. Herein, layered vanadium oxide Mgx V2 O5 ·nH2 O is used as a calcium battery cathode, and it exhibits a high capacity of 195.5 mA h g-1 at 20 mA g-1 and an outstanding cycling life (93.6% capacity retention after 2500 cycles at 1 A g-1 ). Combining theoretical analysis and experimental design, a series of layered oxides (Mx V2 O5 ·nH2 O, M = Mg, Ca, Sr) is selected as a model system to identify the Ca storage mechanism. It is found that the hydrated alkaline earth metal ions in the vanadium-based layered oxide interlayers play a critical role as pillared stabilizers to facilitate Ca2+ insertion/extraction. Compared with Ca2+ and Sr2+ , the presence of Mg2+ provides vanadium oxides with a rigid framework that allows for minimized volume fluctuation (a tiny variation of ≈0.15 Å of the interlayer spacing). Such an understanding of the Ca storage mechanism is a key step in the rational design and selection of materials for calcium batteries to achieve a high capacity and long cycle life.