Highly Crystalline Multivariate Prussian Blue Analogs via Equilibrium Chelation Strategy for Stable and Fast Charging Sodium-Ion Batteries.

Prussian blue analogs (PBAs) have been widely recognized as superior cathode materials for sodium-ion batteries (SIBs) owing to numerous merits. However, originating from the rapid crystal growth, PBAs still suffer from considerable vacancy defects and interstitial water, making the preparation of long-cycle-life PBAs the greatest challenge for its practical application. Herein, a novel equilibrium chelation strategy is first proposed to synthesize a high crystallinity (94.7%) PBAs, which is realized by modulating the chelating potency of strong chelating agents via "acid effect" to achieve a moderate chelating effect, forcefully breaking through the bottleneck of poor cyclic stability for PBAs cathodes. Impressively, the as-prepared highly crystalline PBAs represent an unprecedented level of electrochemical performance including ultra-long lifespan (10000 cycles with 86.32% capacity maintenance at 6 A g-1), excellent rate capability (82.0 mAh g-1 at 6 A g-1). Meanwhile, by pairing with commercial hard carbon, the as-prepared PBAs-based SIBs exhibit high energy density (350 Wh kg-1) and excellent capacity retention (82.4% after 1500 cycles), highlighting its promising potential for large-scale energy storage applications.

Enabling Rapid and Stable Sodium Storage via a P2-Type Layered Cathode with High-Voltage Zero-Phase Transition Behavior.

Currently, a major target in the development of Na-ion batteries is the concurrent attainment of high-rate capacity and long cycling stability. Herein, an advanced Na-ion battery with high-rate capability and long cycle stability based on Li/Ti co-doped P2-type Na0.67Mn0.67Ni0.33O2, a host material with high-voltage zero-phase transition behavior and fast Na+ migration/conductivity during dynamic de-embedding process, is constructed. Experimental results and theoretical calculations reveal that the two-element doping strategy promotes a mutually reinforcing effect, which greatly facilitates the transfer capability of Na+. The cation Ti4+ doping is a dominant high voltage, significantly elevating the operation voltage to 4.4 V. Meanwhile, doping Li+ shows the function in charge transfer, improving the rate performance and prolonging cycling lifespan. Consequently, the designed P2-Na0.75Mn0.54Ni0.27Li0.14Ti0.05O2 cathode material exhibits discharge capacities of 129, 104, and 85 mAh g- 1 under high voltage of 4.4 V at 1, 10, and 20 C, respectively. More importantly, the full-cell delivers a high initial capacity of 198 mAh g-1 at 0.1 C (17.3 mA g-1) and a capacity retention of 73% at 5 C (865 mA g-1) after 1000 cycles, which is seldom witnessed in previous reports, emphasizing their potential applications in advanced energy storage.

A Disordered Rubik's Cube-Inspired Framework for Sodium-Ion Batteries with Ultralong Cycle Lifespan.

Sodium-ion batteries (SIBs) with fast-charge capability and long lifespan could be applied in various sustainable energy storage systems, from personal devices to grid storage. Inspired by the disordered Rubik's cube, here, we report that the high-entropy (HE) concept can lead to a very substantial improvement in the sodium storage properties of hexacyanoferrate (HCF). An example of HE-HCF has been synthesized as a proof of concept, which has achieved impressive cycling stability over 50 000 cycles and an outstanding fast-charging capability up to 75 C. Remarkable air stability and all-climate performance are observed. Its quasi-zero-strain reaction mechanism and high sodium diffusion coefficient have been measured and analyzed by multiple in situ techniques and density functional theory calculations. This strategy provides new insights into the development of advanced electrodes and provides the opportunity to tune electrochemical performance by tailoring the atomic composition.

3 D Porous CoS2 Hexadecahedron Derived from MOC toward Ultrafast and Long-Lifespan Lithium Storage.

A new hexadecahedron assembled by core-shell CoS2 particles@N-doped carbon (CoS2 @NCH) is prepared successfully through the self-templating method. The CoS2 @NCH hybrid electrode delivers a high lithium-storage capacity of 778 mA h g-1 after 1000 cycles at a high current density of 1 A g-1 , which is the longest cycle lifespan among the reported CoS2 anode materials in lithium-ion batteries. Furthermore, the CoS2 @NCH hybrid electrode shows excellent rate capability with a discharge capacity of 220 mA h g-1 at an extremely high current density of 20 A g-1 , and a charge capacity of 649 mA h g-1 is restored upon returning the current density back to 2 A g-1 . The superior performance is attributed to the unique construction of CoS2 @NCH. The N-doped interconnected porous carbon shells form highly conductive skeletons for quick electron transfer and prevent the electrode from collapsing. Moreover, the porous characteristic of the materials plays a key role: as some effective channels, the mesopores on the porous carbon shells provide greater access for lithium, and the mesopores derived from the particle interspace enables the complete immersion of the electrodes in electrolyte, which alleviates the volume expansion and ensures the integrity of the electrode. In addition, the nanosized CoS2 particles, which shorten the ion-transport path and provide extra electroactive sites, also improve the reaction kinetics.

High Rate, Long Lifespan LiV3 O8 Nanorods as a Cathode Material for Lithium-Ion Batteries.

LiV3 O8 nanorods with controlled size are successfully synthesized using a nonionic triblock surfactant Pluronic-F127 as the structure directing agent. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy techniques are used to characterize the samples. It is observed that the nanorods with a length of 4-8 µm and diameter of 0.5-1.0 µm distribute uniformly. The resultant LiV3 O8 nanorods show much better performance as cathode materials in lithium-ion batteries than normal LiV3 O8 nanoparticles, which is associated with the their unique micro-nano-like structure that can not only facilitate fast lithium ion transport, but also withstand erosion from electrolytes. The high discharge capacity (292.0 mAh g-1 at 100 mA g-1 ), high rate capability (138.4 mAh g-1 at 6.4 A g-1 ), and long lifespan (capacity retention of 80.5% after 500 cycles) suggest the potential use of LiV3 O8 nanorods as alternative cathode materials for high-power and long-life lithium ion batteries. In particular, the synthetic strategy may open new routes toward the facile fabrication of nanostructured vanadium-based compounds for energy storage applications.

Plant secondary metabolites involved in the stress tolerance of long-lived trees.

Ancient trees are natural wonders because of their longevity, having lived for hundreds or thousands of years, and their ability to withstand changing environments and a variety of stresses. These long-lived trees have sophisticated defense mechanisms, such as the production of specialized plant metabolites (SPMs). In this review, we provide an overview of the major biotic and abiotic stresses that long-lived trees often face, as well as an analysis of renowned ancient tree species and their unique protective SPMs against environmental stressors. We also discuss the synthesis and accumulation of defensive SPMs induced by environmental factors and endophytes in these trees. Furthermore, we conducted a comparative genomic analysis of 17 long-lived tree species and discovered significant expansions of SPM biosynthesis gene families in these species. Our comprehensive review reveals the crucial role of SPMs in high resistance in long-lived trees, providing a novel natural resource for plant defense, crop improvement and even the pharmaceutical industry.

Micron-Sized Cobalt Niobium Oxide with Multiscale Porous Sponge-Like Structure Boosting High-Rate and Long-Life Lithium Storage.

Niobium-based oxides show great potential as intercalation-type anodes in lithium-ion batteries due to their relatively high theoretical specific capacity. Nevertheless, their electrochemical properties are unsatisfactorily restricted by the poor electronic conductivity. Here, micron-sized Co0.5Nb24.5O62 with multiscale sponge-like structure is synthesized and demonstrated to be a fast-charging anode material. It can deliver a remarkable capacity of 287 mA h g-1 with a safe average working potential of ≈1.55 V vs Li+/Li and a high initial Coulombic efficiency of 91.1% at 0.1C. Owing to the fast electronic/ionic transport derived from the multiscale porous sponge-like structure, Co0.5Nb24.5O62 exhibits a superior rate capability of 142 mA h g-1 even at 10C. In addition, its maximum volume change during the charge/discharge process is determined to be 9.18%, thus exhibiting excellent cycling stability with 75.3% capacity retention even after 3000 cycles at 10C. The LiFePO4//Co0.5Nb24.5O62 full cells also achieve good rate performance of 101 mA h g-1 at 10C, as well as an excellent cycling performance of 81% capacity retention after 1200 cycles at 5C, further proving the promising application prospect of Co0.5Nb24.5O62.

Liquid Bi-Sb-Sn Electrodes with Synergistic Stabilization Mechanism for Long-Lifespan Sodium-Based Liquid Metal Batteries.

Sodium-based liquid metal batteries are well suited for stationary energy storage due to their long life, intrinsic safety, and ease of scale-up. However, the irreversible alloying reaction between the positive current collector (PCC) and the cathodes at high temperatures leads to severe capacity degradation of the battery, severely limiting its scale-up application. In this work, a Bi-Sb-Sn alloy cathode based on a synergistic stabilization mechanism was designed for the first time. Due to the density difference of Bi, Sb, and Sn and the compatibility difference of Bi and Sn with the PCC, a part of Bi and Sn is spontaneously distributed in the region close to the PCC. The protection of Sb is realized by blocking the contact of Sb with the PCC as well as removing the PCC material dissolved in the cathode to prevent the loss of active material. Based on such protection, the Na||Bi36Sb24Sn40 cell maintained 99% Coulombic efficiency for 450 cycles at a rate of 0.75 C, with a capacity retention of 99.56% and a capacity decay rate of 0.001% per cycle. In addition, the interaction of Bi, Sb, and Sn during discharge also promotes capacity release and energy efficiency. At 0.3 C, the Na||Bi36Sb24Sn40 cell achieved 89% capacity utilization and 82% energy efficiency. These results provide an idea for the design of other batteries based on liquid metal electrodes.

Rational design of nitrogen (N), boron (B), and phosphorous (P) tri-doped carbon nano-spheres as advanced anode materials for sodium-ion batteries with an ultra-long lifespan.

Developing improved anode materials is critical to the performance enhancement and the lifespan prolonging of sodium-ion batteries (SIBs). In this context, carbon-based nanostructures have emerged as a promising candidate. In this work, we have synthesized N, B, and P tri-doped carbon (NBPC) spheres using a one-step carbonization method. The as-prepared NBPC exhibits exceptional properties, including an expanded layer space, sufficient structural defects, and enhanced electrical conductivity. These characteristics synergistically contribute to the remarkable rate capability and ultra-long lifespan when NBPC is employed as an anode material for SIBs. The as-prepared NBPC demonstrates a reversible capacity of 290.6 mAh/g at 0.05 A/g, with a capacity retention of 98.4% after 800 cycles. Furthermore, NBPC exhibits an impressively ultra-long cycle life of 2400 cycles at 1.0 A/g with a reversible capacity of 140.2 mAh/g. First principle calculations confirm that the introduction of N, B, and P heteroatoms in carbon enhances the binding strength of sodium ions within NBPC. This work presents a novel approach for fabricating advanced anode materials, enabling the development of long-life SIBs for practical applications.

Amorphous Heterostructure Derived from Divalent Manganese Borate for Ultrastable and Ultrafast Aqueous Zinc Ion Storage.

Aqueous zinc-manganese (Zn-Mn) batteries have promising potential in large-scale energy storage applications since they are highly safe, environment-friendly, and low-cost. However, the practicality of Mn-based materials is plagued by their structural collapse and uncertain energy storage mechanism upon cycling. Herein, this work designs an amorphous manganese borate (a-MnBOx ) material via disordered coordination to alleviate the above issues and improve the electrochemical performance of Zn-Mn batteries. The unique physicochemical characteristic of a-MnBOx enables the inner a-MnBOx to serve as a robust framework in the initial energy storage process. Additionally, the amorphous manganese dioxide, amorphous Znx MnO(OH)2 , and Zn4 SO4 (OH)6 ·4H2 O active components form on the surface of a-MnBOx during the charge/discharge process. The detailed in situ/ex situ characterization demonstrates that the heterostructure of the inner a-MnBOx and surface multicomponent phases endows two energy storage modes (Zn2+ /H+ intercalation/deintercalation process and reversible conversion mechanism between the Znx MnO(OH)2 and Zn4 SO4 (OH)6 ·4H2 O) phases). Therefore, the obtained Zn//a-MnBOx battery exhibits a high specific capacity of 360.4 mAh g-1 , a high energy density of 484.2 Wh kg-1 , and impressive cycling stability (97.0% capacity retention after 10 000 cycles). This finding on a-MnBOx with a dual-energy storage mechanism provides new opportunities for developing high-performance aqueous Zn-Mn batteries.

Progressive activation of porous vanadium nitride microspheres with intercalation-conversion reactions toward high performance over a wide temperature range for zinc-ion batteries.

Rechargeable aqueous zinc-ion batteries have great promise for becoming next-generation storage systems, although the irreversible intercalation of Zn2+ and sluggish reaction kinetics impede their wide application. Therefore, it is urgent to develop highly reversible zinc-ion batteries. In this work, we modulate the morphology of vanadium nitride (VN) with different molar amounts of cetyltrimethylammonium bromide (CTAB). The optimal electrode has porous architecture and excellent electrical conductivity, which can alleviate volume expansion/contraction and allow for fast ion transmission during the Zn2+ storage process. Furthermore, the CTAB-modified VN cathode undergoes a phase transition that provides a better framework for vanadium oxide (VOx). With the same mass of VN and VOx, VN provides more active material after phase conversion due to the molar mass of the N atom being less than that of the O atom, thus increasing the capacity. As expected, the cathode displays an excellent electrochemical performance of 272 mAh g-1 at 5 A g-1, high cycling stability up to 7000 cycles, and excellent performance over a wide temperature range. This discovery creates new possibilities for the development of high-performance multivalent ion aqueous cathodes with rapid reaction mechanisms.

Dual-Type Carbon Confinement Strategy: Improving the Stability of CoTe2 Nanocrystals for Sodium-Ion Batteries with a Long Lifespan.

Sodium-ion batteries have great potential to become large-scale energy storage devices due to their abundant and low-cost resources. However, the lack of anode and cathode materials with both high energy density and long-term cycling performance significantly affects their commercial applications. In this work, uniform CoTe2 nanoparticles are generated from the tellurization of Co nanoparticles, which were coated with polyvinylpyrrolidone in a three-dimensional (3D) porous carbon matrix (CoTe2@3DPNC). Finally, a dual-type carbon confinement structure is formed after tellurization during which citric acid is adopted as the source of the inner carbon scaffold. The hierarchical carbon matrix not only builds a robust and fast ion/electronic conductive 3D architecture but also mitigates the volume expansion and aggregation of CoTe2 during sodium insertion/extraction. Remarkably, the CoTe2@3DPNC electrode displays a high reversible capacity (216.5 mAh g-1/627.9 mAh cm-3 at 0.2 A g-1 after 200 cycles) and outstanding long-term cycling performance (118.1 mAh g-1/342.5 mAh cm-3 even at 5.0 A g-1 after 2500 cycles). Kinetics tests and capacitance calculations clearly reveal a battery-capacitive dual-model Na-storage mechanism. Furthermore, ex situ XRD/SEM/TEM demonstrate superior stability during sodium insertion/extraction. This work provides a valuable strategy for the rational structural design of long-life electrodes for advanced rechargeable batteries.

Rational Design of an Artificial SEI: Alloy/Solid Electrolyte Hybrid Layer for a Highly Reversible Na and K Metal Anode.

The practical application of a Na/K-metallic anode is intrinsically hindered by the poor cycle life and safety issues due to the unstable electrode/electrolyte interface and uncontrolled dendrite growth during cycling. Herein, we solve these issues through an in situ reaction of an oxyhalogenide (BiOCl) and Na to construct an artificial solid electrolyte interphase (SEI) layer consisting of an alloy (Na3Bi) and a solid electrolyte (Na3OCl) on the surface of the Na anode. As demonstrated by theoretical and experimental results, such an artificial SEI layer combines the synergistic properties of high ionic conductivity, electronic insulation, and interfacial stability, leading to uniform dendrite-free Na deposition beneath the hybrid SEI layer. The protected Na anode presents a low voltage polarization of 30 mV, achieving an extended cycling life of 700 h at 1 mA cm-2 in the carbonate-based electrolyte. The full cell based on the Na3V2(PO4)3 cathode and hybrid SEI-protected Na anode shows long-term stability. When this strategy is applied to a K metal anode, the protected K anode also reaches a cycling life of over 4000 h at 0.5 mA cm-2 with a low voltage polarization of 100 mV. Our work provides an important insight into the design principles of a stable artificial SEI layer for high-energy-density metal batteries.

All-climate aqueous Na-ion batteries using "water-in-salt" electrolyte.

Aqueous Na-ion batteries have been extensively studied for large-scale energy storage systems. However, their wide application is still limited by their inferior cycle stability (<3000 cycles) and poor temperature tolerance. Furthermore, many of the reported high rate behaviors are achieved at a low mass loading (<3 mg cm-2) of the electrodes. Herein, we propose an aqueous Na-ion battery which includes a Ni-based Prussian blue (NiHCF) cathode, a carbonyl-based organic compound, 5,7,12,14-pentacenetetrone (PT) anode and a "water-in-salt" electrolyte (17 mol kg-1 NaClO4 in water). Its operation involves the reversible coordination reaction of the PT anode and the extraction/insertion of Na+ in the NiHCF cathode. It is demonstrated that the wide internal spaces of the PT anode and NiHCF cathode can not only buffer the volumetric change induced by Na+ storage, but also enable fast kinetics. The full cell exhibits a supercapacitor-like rate performance of 50 A g-1 (corresponding to a discharge or charge within 6.3 s) and a super-long lifespan of 15,000 cycles. Moreover, the excellent rate performance can still be preserved even with a high mass loading of the electrodes (15 mgNiHCF cm-2 and 8 mgPT cm-2). Especially, the cell can work well in a wide temperature range, from -40 to 100 °C, showing a typical all-climate operation.

In Situ Construction a Stable Protective Layer in Polymer Electrolyte for Ultralong Lifespan Solid-State Lithium Metal Batteries.

Solid-state lithium metal batteries (SLMBs) are attracting enormous attention due to their enhanced safety and high theoretical energy density. However, the alkali lithium with high reducibility can react with the solid-state electrolytes resulting in the inferior cycle lifespan. Herein, inspired by the idea of interface design, the 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide as an initiator to generate an artificial protective layer in polymer electrolyte is selected. Time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy reveal the stable solid electrolyte interface (SEI) is in situ formed between the electrolyte/Li interface. Scanning electron microscopy (SEM) images demonstrate that the constructed SEI can promote homogeneous Li deposition. As a result, the Li/Li symmetrical cells enable stable cycle ultralong-term for over 4500 h. Moreover, the as-prepared LiFePO4 /Li SLMBs exhibit an impressive ultra-long cycle lifespan over 1300 cycles at 1 C, as well as 1600 cycles at 0.5 C with a capacity retention ratio over 80%. This work offers an effective strategy for the construction of the stable electrolyte/Li interface, paving the way for the rapid development of long lifespan SLMBs.

Scalable One-Pot Synthesis of Hierarchical Bi@C Bulk with Superior Lithium-Ion Storage Performances.

Lithium-ion batteries (LIBs), the most successful commercial energy storage devices, are now widespread in our daily life. However, the lack of appropriate electrode materials with long lifespan and superior rate capability is the urgent bottleneck for the development of high-performance LIBs. Herein, a hierarchical Bi@C bulk is developed via a scalable pyrolysis method. Due to the ultrafine size of Bi nanoparticles and in situ generated porous carbon framework, this Bi@C anode evidently facilitates the diffusion of Li+/electron, availably inhibits the agglomeration of active nano-Bi, and effectively mitigates the volume fluctuation. This hierarchical Bi@C bulk exhibits stable cycling performance for both LIBs (256 mAh g-1 at 1.0 A g-1 over 1400 cycles) and potassium-ion batteries (271 mAh g-1 at 0.1 A g-1 for 200 cycles). More importantly, when coupled with a commercial LiCoO2 cathode, the assembled LiCoO2//Bi@C cells provide an output voltage of 2.9 V and retain a capacity of 202 mAh g-1 at 0.15 A g-1. Moreover, kinetic analysis and in situ X-ray diffraction characterization reveal that the Bi@C anode displays a dominated pseudocapacitance behavior and a typical alloying storage mechanism during the cycling process.

Engineering 3D Well-Interconnected Na4MnV(PO4)3 Facilitates Ultrafast and Ultrastable Sodium Storage.

Na4MnV(PO4)3 (denoted as NMVP) has drawn increasing attention owing to the three-dimensional framework and high theoretical capacity. Nevertheless, the inherent low electronic conductivity of NMVP impedes the scale-up commercial applications. In this work, the feasibility to achieve ultrahigh-rate capability and long lifespan by in situ embedding the intertwined carbon nanotube (CNT) matrix into the bulk of Na4MnV(PO4)3@C composites through a facile wet-chemical approach is reported. The elaborately prepared Na4MnV(PO4)3@C@CNTs cathode delivers a discharge capacity of 109.9 mA h g-1 at C/5 with an impressive rate capability of 68.9 mA h g-1 at an ultrahigh current rate of 90 C as well as a fascinating cycling performance of 68.3% capacity retention at 40 C after 4000 cycles. The optimum design of the 3D well-interconnected NMVP permitting fast kinetics for transported Na+/e- is beneficial to the excellent electrochemical performance, which is further studied by the galvanostatic intermittent titration technique, cyclic voltammetry, and electrochemical impedance spectra measurements. The pseudocapacitance contributions are also investigated. The research demonstrates that the dual-nanocarbon synergistically modified NMVP composite is expected to facilitate the commercialization of sodium-ion batteries.

Is Longevity a Heritable Trait? Evidence for Non-genomic Influence from an Extended Longevity Phenotype of Drosophila melanogaster.

BACKGROUND: Although genetic variations are heritable, some quantitative traits like longevity may have non-genomic influence on heritability. Laboratory-selected inbred strains of extended longevity phenotype of Drosophila offer an opportunity to study the inheritance of longevity. OBJECTIVE: The aim of the study was to examine the heritability of longevity in an extended longevity phenotype of Drosophila melanogaster using reciprocal cross effects in F1 and F2 generations. METHODS: Lifespan variations of virgin and mated flies in parent, F1 and F2 generations were investigated using reciprocal crosses between normal and long lifespan lines of inbred population of D. melanogaster. Heterosis, narrow-sense heritability, recombination loss, maternal effect and overdominance with respect to survivorship in virgin and mated flies were analyzed. RESULTS: Virgin flies lived longer than mated flies. There was no significant effect of mid-parent heterosis, recombination loss and overdominance on variations in longevity, whereas, significant maternal effect and narrow-sense heritability were observed in mated and virgin flies, respectively. CONCLUSION: Absence of heterosis in our study population of Drosophila phenotypes could be due to the lack of genetic heterogeneity. The heritability of the longevity trait in an inbred extended longevity phenotype depends on the variations in genetic and environmental factors.

Amorphous mesoporous GeO x anode for Na-ion batteries with high capacity and long lifespan.

It is recently demonstrated that amorphous Ge anode shows higher reversible Na-ion storage capacity (590 mA h g-1) than crystallized Ge anode (369 mA h g-1). Here, amorphous GeO x anode is prepared by a simple wet-chemistry reduction route at room temperature. The obtained amorphous GeO x shows a porous hierarchical architecture, accompanied with a Brunauer-Emmett-Teller surface area of 159 m2 g-1 and an average pore diameter of 14 nm. This unique structure enables the GeO x anode to enhance the Na-ion/electron diffusion rate, and buffer the volume change. As anode for Na-ion battery, high reversible capacity over 400 mA h g-1, fine rate capability with a capacity of 200 mA h g-1 maintained at 3.0 A g-1 and long-term cycling stability with 270 mA h g-1 even over 1000 cycles at 1.0 A g-1 are obtained.