Although ether‐based electrolytes have been extensively applied in anode evaluation of batteries, anodic instability arising from solvent oxidability is always a tremendous obstacle to matching with ...high‐voltage cathodes. Herein, by rational design for solvation configuration, the fully coordinated ether‐based electrolyte with strong resistance against oxidation is reported, which remains anodically stable with high‐voltage Na3V2(PO4)2O2F (NVPF) cathode under 4.5 V (versus Na+/Na) protected by an effective interphase. The assembled graphite//NVPF full cells display superior rate performance and unprecedented cycling stability. Beyond that, the constructed full cells coupling the high‐voltage NVPF cathode with hard carbon anode exhibit outstanding electrochemical performances in terms of high average output voltage up to 3.72 V, long‐term cycle life (such as 95 % capacity retention after 700 cycles) and high energy density (247 Wh kg−1). In short, the optimized ether‐based electrolyte enriches systematic options, the ability to maintain oxidative stability and compatibility with various anodes, exhibiting attractive prospects for application.
By rational design of the solvation configuration, a cation–solvent fully coordinated ether‐based electrolyte with strong oxidation resistance up to 4.5 V (versus Na+/Na) was developed and applied in graphite//NVPF and LHC//NVPF full cells which showed superior rate performance and unprecedented cycling stability.
Impossible voltage plateau regulation for the cathode materials with fixed active elemental center is a pressing issue hindering the development of Na‐superionic‐conductor (NASICON)‐type ...Na3V2(PO4)2F3 (NVPF) cathodes in sodium‐ion batteries (SIBs). Herein, a high‐entropy substitution strategy, to alter the detailed crystal structure of NVPF without changing the central active V atom, is pioneeringly utilized, achieving simultaneous electronic conductivity enhancement and diffusion barrier reduction for Na+, according to theoretical calculations. The as‐prepared carbon‐free high‐entropy Na3V1.9(Ca,Mg,Al,Cr,Mn)0.1(PO4)2F3 (HE‐NVPF) cathode can deliver higher mean voltage of 3.81 V and more advantageous energy density up to 445.5 Wh kg−1, which is attributed by the diverse transition‐metal elemental substitution in high‐entropy crystalline. More importantly, high‐entropy introduction can help realize disordered rearrangement of Na+ at Na(2) active sites, thereby to refrain from unfavorable discharging behaviors at low‐voltage region, further lifting up the mean working voltage to realize a full Na‐ion storage at the high voltage plateau. Coupling with a hard carbon (HC) anode, HE‐NVPF//HC SIB full cells can deliver high specific energy density of 326.8 Wh kg−1 at 5 C with the power density of 2178.9 W kg−1. This route means the unlikely potential regulation in NASICON‐type crystal with unchangeable active center becomes possible, inspiring new ideas on elevating the mean working voltage for SIB cathodes.
A high‐entropy effect is delicately introduced into fluorophosphate cathode for sodium‐ion batteries by in situ partial substitution of active V central atom, preparing a high‐entropy carbon‐free Na3V1.9(Ca,Mg,Al,Cr,Mn)0.1(PO4)2F3 cathode, suppressing the occurrence of detrimental phase transition process in the low‐voltage region, and further lifting up the mean working voltage of pristine Na3V2(PO4)2F3, enhancing sodium storage behavior, rate capability, and cycle performance.
Relatively low reactivity hinders using chlorodifluoromethane (ClCF
H) for general difluoromethylation with organic molecules, despite its availability as an inexpensive industrial chemical. To date, ...transformations of ClCF
H are very limited and most of them involve difluorocarbene intermediate. Here, we describe a strategy for difluoromethylation of aromatics through nickel-catalyzed cross-coupling of ClCF
H with readily accessible (hetero)aryl chlorides. The reaction proceeds under mild reaction conditions with high efficiency and features synthetic simplicity without preformation of arylmetals and broad substrate scope, including a variety of heteroaromatics and commercially available pharmaceuticals. The reliable practicability and scalability of the current nickel-catalyzed process has also been demonstrated by several 10-g scale reactions without loss of reaction efficiency. Preliminary mechanistic studies reveal that the reaction starts from the oxidative addition of aryl chlorides to Ni(0) and a difluoromethyl radical is involved in the reaction, providing a route for applications of ClCF
H in organic synthesis and related chemistry.
Conventional ion batteries utilizing metallic ions as the single charge carriers are limited by the insufficient abundance of metal resources. Although supercapacitors apply both cations and anions ...to store energy through absorption and/or Faradic reactions occurring at the interfaces of the electrode/electrolyte, the inherent low energy density hinders its application. The graphite‐cathode‐based dual‐ion battery possesses a higher energy density due to its high working potential of nearly 5 V. However, such a battery configuration suffers from severe electrolyte decomposition and exfoliation of the graphite cathode, rendering an inferior cycle life. Herein, a new surface‐modification strategy is developed to protect the graphite cathode from the anion salvation effect and the deposition derived from electrolyte decomposition by generating an artificial solid electrolyte interphase (SEI). Such SEI‐modified graphite exhibits superior cycling stability with 96% capacity retention after 500 cycles under 200 mA g−1 at the upper cutoff voltage of 5.0 V, which is much improved compared with the pristine graphite electrode. Through several ex situ studies, it is revealed that the artificial SEI greatly stabilizes the interfaces of the electrode/electrolyte after reconstruction and gradual establishment of the optimal anion‐transport path. The findings shed light on a new avenue toward promoting the performance of the dual‐ion battery (DIB) and hence to make it practical finally.
An artificial layer of a solid electrolyte interphase is fabricated on a graphite cathode for a dual‐ion battery (DIB). Such surface modification can alleviate the electrolyte decomposition at the high working voltage of the anion de‐/intercalation processes and the solvation effect of anions, much improving the cycling stability of the Li//graphite DIB.
Dual‐ion batteries (DIBs) are a viable option for large‐scale energy storage owing to their high energy density, low cost, and environmental friendliness. However, interfacial instability at both the ...cathode and anode in Li‐graphite DIBs (LG‐DIBs) contributes to poor cycling performance and failed energy storage, severely limiting their application potentials. Herein, a two‐pronged strategy is used to improve the interfacial stability, synergistically stabilizing the graphite cathode by applying a rigid/inert surface coating while building a 3D framework on the lithium anode. The resultant LG‐DIBs are ultrastable and achieve a long cycle life (capacity retention of 80% after 2700 cycles at 200 mA−1) in the all‐climate temperature range from −25 to 40 °C. Ex situ characterization reveals that the cathode–electrolyte interphase on graphite is stabilized by suppressing the electrolyte decomposition and reducing graphite exfoliation. Simultaneously, the framework constructed on the lithium anode induces uniform and dendrite‐free Li deposition owing to its 3D structure. This study not only contributes to the development of practical LG‐DIBs but also points out a promising research direction for other new types of batteries.
A two‐pronged approach is adopted to modify and strengthen the anode electrolyte interphase and cathode electrolyte interphase synergistically in Li‐graphite dual‐ion batteries. The battery life is significantly enhanced in all climates from −25 to 40 °C by inducing homogeneous Li deposition and suppressing successive decomposition of the electrolyte on the graphite cathode.
Summary
Root anatomy plays important roles in the control of leaf water relations. However, few studies have evaluated whether and how anatomical traits of absorptive roots influence leaf physiology ...of herbaceous species in a temperate grassland.
We measured absorptive root anatomical traits and leaf physiological traits of 15 herbaceous species in a temperate steppe and monitored their responses to increased precipitation in a field stimulating experiment.
Root anatomical and leaf physiological traits differed among monocotyledonous grasses, monocotyledonous liliaceous species and dicotyledonous forbs. The species with higher stele: root diameter, lower root diameter and cortex thickness exhibited higher transpiration rates and stomatal conductance, but lower intrinsic water‐use efficiency. Increased precipitation enhanced transpiration and stomatal conductance of forbs and lilies, but it enhanced photosynthesis in lilies exclusively. The sensitive response of lilies to precipitation may be related to their large root diameter and cortex thickness.
In summary, we observed distinct differences in anatomical traits of absorptive roots among plant groups in temperate steppes. These differences drove variations in leaf physiological traits and their diverse responses to precipitation change. These findings highlight the important roles of root anatomical traits in driving leaf‐level physiological processes in temperate grasslands.
See also the Commentary on this article by Long & Medeiros, 229: 1186–1188.
Incorporation of N,S‐codoped nanotube‐like carbon (N,S‐NTC) can endow electrode materials with superior electrochemical properties owing to the unique nanoarchitecture and improved kinetics. Herein, ...α‐MnS nanoparticles (NPs) are in situ encapsulated into N,S‐NTC, preparing an advanced anode material (α‐MnS@N,S‐NTC) for lithium‐ion/sodium‐ion batteries (LIBs/SIBs). It is for the first time revealed that electrochemical α → β phase transition of MnS NPs during the 1st cycle effectively promotes Li‐storage properties, which is deduced by the studies of ex situ X‐ray diffraction/high‐resolution transmission electron microscopy and electrode kinetics. As a result, the optimized α‐MnS@N,S‐NTC electrode delivers a high Li‐storage capacity (1415 mA h g−1 at 50 mA g−1), excellent rate capability (430 mA h g−1 at 10 A g−1), and long‐term cycling stability (no obvious capacity decay over 5000 cycles at 1 A g−1) with retained morphology. In addition, the N,S‐NTC‐based encapsulation plays the key roles on enhancing the electrochemical properties due to its high conductivity and unique 1D nanoarchitecture with excellent protective effects to active MnS NPs. Furthermore, α‐MnS@N,S‐NTC also delivers high Na‐storage capacity (536 mA h g−1 at 50 mA g−1) without the occurrence of such α → β phase transition and excellent full‐cell performances as coupling with commercial LiFePO4 and LiNi0.6Co0.2Mn0.2O2 cathodes in LIBs as well as Na3V2(PO4)2O2F cathode in SIBs.
α‐MnS nanoparticles are in situ encapsulated into N,S‐codoped nanotube‐like carbon (α‐MnS@N,S‐NTC) as an advanced anode for Li/Na‐ion batteries. The α → β phase transition during the 1st cycle in LIBs is for the first time revealed by ex situ X‐ray diffraction and high‐resolution transmission electron microscopy studies, which improves the electrode kinetics and Li‐storage properties. α‐MnS@N,S‐NTC also exhibits superior performance in Li/Na‐ion half/full cells.
Transition‐metal‐catalyzed difluoroalkylation of aromatics remains challenging despite the importance of difluoroalkylated arenes in medicinal chemistry. Herein, the first successful example of ...nickel‐catalyzed difluoroalkylation of aryl boronic acids is described. The reaction allows access to a variety of functionalized difluoromethyl bromides and chlorides, and paves the way to highly cost‐efficient synthesis of a wide range of difluoroalkylated arenes. The notable features of this protocol are its high generality, excellent functional‐group compatibility, low‐cost nickel‐catalyst, and practicality for gram‐scale production, thus providing a facile method for applications in drug discovery and development.
Simple and easy: The first example of a nickel‐catalyzed difluoroalkylation of aryl boronic acids with functionalized difluoromethyl bromides and chlorides has been developed. This cross‐coupling process features a broad substrate scope, a cheap catalyst, and excellent functional‐group compatibility.
As promising cathode for sodium‐ion batteries, Na+ Superionic Conductor (NASICON)‐type materials have attracted attention owing to their excellent structural stability, superior ionic conductivity, ...and small volume expansion. However, the vanadium‐based NASICON‐type cathode with the biotoxicity and exorbitant price of V element and the iron‐based cathode with low mean working voltage as well as the intrinsic poor electronic conductivity of polyanionic compounds hinder their practical applications. Herein, a double‐carbon‐layer decorated heterogeneous composite, Na3V2(PO4)3‐Na3Fe2(PO4)(P2O7) (NVFPP/C/G), is successfully prepared for addressing these limitations. Due to their synergistic effect, NVFPP/C/G exhibits excellent electrochemical performance in half‐cell system and superior full‐cell performance when matched with hard carbon anode. Furthermore, the phase composition, electrode kinetics, and phase transition are confirmed by combined analyses of slow scanning power X‐ray diffraction, high‐resolution transmission electron microscopy, cyclic voltammetry with various scan rates, galvanostatic intermittent titration technique, ex situ X‐ray photoelectron spectra, and in situ X‐ray diffraction. This study portends a promising strategy to utilize composite structure engineering for developing advanced polyanionic cathodes.
A double‐carbon‐layer decorated heterogeneous Na3V2(PO4)3‐Na3Fe2(PO4)(P2O7) composite is proposed as cathode for sodium‐ion batteries. Due to the synergistic effect, it exhibits excellent electrochemical performance in half‐cell system and superior full‐cell performance. The heterogeneous composite structure engineering strategy provides a new approach to design high‐performance polyanionic cathodes for batteries.
Current efforts in the proteolysis targeting chimera (PROTAC) field mostly focus on choosing an appropriate E3 ligase for the target protein, improving the binding affinities towards the target ...protein and the E3 ligase, and optimizing the PROTAC linker. However, due to the large molecular weights of PROTACs, their cellular uptake remains an issue. Through comparing how different warhead chemistry, reversible noncovalent (RNC), reversible covalent (RC), and irreversible covalent (IRC) binders, affects the degradation of Bruton's Tyrosine Kinase (BTK), we serendipitously discover that cyano-acrylamide-based reversible covalent chemistry can significantly enhance the intracellular accumulation and target engagement of PROTACs and develop RC-1 as a reversible covalent BTK PROTAC with a high target occupancy as its corresponding kinase inhibitor and effectiveness as a dual functional inhibitor and degrader, a different mechanism-of-action for PROTACs. Importantly, this reversible covalent strategy is generalizable to improve other PROTACs, opening a path to enhance PROTAC efficacy.
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