Transition metal selenides have been attracting significant attention owing to their high conductivity and theoretical capacity. In this article, the N‐doped carbon (NDC)‐coated Ni1.8Co1.2Se4 ...nanoparticles encapsulated in NDC nanoboxes are prepared from the bi‐metal organic framework (Ni3Co(CN)62·6H2O, Ni‐Co BMOF) after the selenization reaction and carbon coating. When used as an anode material for sodium‐ion batteries, the prepared anode material delivers excellent rate performance (211 and 153 mA h g−1 at ultrahigh current densities of 30 and 50 A g−1, respectively) and good cycling performance (379.3 mA h g−1 at 0.5 A g−1 after 100 cycles). More importantly, it also exhibits superior sodium‐ion full cell (SIFC) performance when coupled with a high‐voltage Na3V2(PO4)2O2F cathode recently self‐made by the authors. The fabricated SIFC gives an energy density up to 227 W h kg−1 and the capacity retention of above 97.6% even after 60 cycles at 0.4 A g−1 in a voltage range of 1.2–4.3 V at 25 °C. Moreover, the low‐temperature (from 25 to −25 °C) Na‐storage performance of the fabricated SIFC is also studied.
An advanced anode material with outstanding high‐rate and low‐temperature properties is developed for sodium‐ion half/full batteries. In it, there exists a 3D conductive network composed of N‐doped dual carbon (NDDC) and abundant void spaces between NDDC and Ni1.8Co1.2Se4 nanoparticles, acting as not only a highway to achieve fast charge transfer but also an effective protector for active Ni1.8Co1.2Se4 material.
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.
To date, liquid metals have been widely applied in many fields such as electronics, mechanical engineering and energy. In the last decade, with a better understanding of the physicochemical ...properties such as low viscosity, good fluidity, high thermal/electrical conductivity and good biocompatibility, gallium and gallium-based low-melting-point (near or below physiological temperature) alloys have attracted considerable attention in bio-related applications. This tutorial review introduces the common performances of liquid metals, highlights their featured properties, as well as summarizes various state-of-the-art bio-applications involving carriers for drug delivery, molecular imaging, cancer therapy and biomedical devices. Challenges for the clinical translation of liquid metals are also discussed.
This tutorial review summarizes the common performances, featured properties and various state-of-the-art biomedical applications of liquid metals.
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.
Cancer immunotherapy, as a paradigm shift in cancer treatment, has recently received tremendous attention. The active cancer vaccination, immune checkpoint blockage (ICB) and chimeric antigen ...receptor (CAR) for T‐cell‐based adoptive cell transfer are among these developments that have achieved a significant increase in patient survival in clinical trials. Despite these advancements, emerging research at the interdisciplinary interface of cancer biology, immunology, bioengineering, and materials science is important to further enhance the therapeutic benefits and reduce side effects. Here, an overview of the latest studies on engineering biomaterials for the enhancement of anticancer immunity is given, including the perspectives of delivery of immunomodulatory therapeutics, engineering immune cells, and constructing immune‐modulating scaffolds. The opportunities and challenges in this field are also discussed.
Cancer immunotherapy has recently received tremendous attention and has created a paradigm shift in the treatment of cancer. An overview of the latest studies on tailoring biomaterials for enhancement of anticancer immunity is presented, including delivery of therapeutics to antigen‐presenting cells, delivery of therapeutics to the tumor microenvironment, engineering of immune cells, and constructing immune scaffolds.
Polyanion‐type phosphate materials are highly promising cathode candidates for next‐generation batteries due to their excellent structural stability during cycling; however, their poor conductivity ...has impeded their development. Isostructural and multivalent anion substitution combined with carbon coating is proposed to greatly improve the electrochemical properties of phosphate cathode in sodium‐ion batteries (SIBs). Specifically, multivalent tetrahedral SiO44− substitute for PO43− in Na3V2(PO4)3 (NVP) lattice, preparing the optimal Na3.1V2(PO4)2.9(SiO4)0.1 with high‐rate capability (delivering a high capacity of 82.5 mAh g−1 even at 20 C) and outstanding cyclic stability (≈98% capacity retention after 500 cycles at 1 C). Theoretical calculation and experimental analyses reveal that the anion‐substituted Na3.1V2(PO4)2.9(SiO4)0.1 reduces the bandgap of NVP lattice and enhanced its structural stability, Na+‐diffusion kinetics and electronic conductivity. This strategy of multivalent and isostructural anion substitution chemistry provides a new insight to develop advanced phosphate cathodes.
Na3+xV2(PO4)3−x(SiO4)x (0 ≤ x ≤ 0.15) cathode materials are prepared via substitution of the inactive PO43− sites in Na3V2(PO4)3 with isostructural SiO44− anions. The substitution effects on crystal structure, electrochemical properties, Na+‐diffusion kinetics and electronic conductivity are systematically investigated. Multivalent and isostructural anionic substitution provides a new strategy for designing polyanionic materials of sodium‐ion batteries.
Polyanionic transition metal polyphosphate (TMPO)‐type Na3V2(PO4)2O2F (NVPO2F) is promising as cathode for large‐scale sodium‐ion batteries (SIBs) on account of its considerable capacity and highly ...stable structure. However, the redox of transition metal and phase transitions along with the (de)intercalation of Na+ lead to its slow kinetics and inferior rate performance. Herein, chlorine (Cl) is applied as a heteropical dopant to obtain Cl‐doped NVPO2F (NVPO2−xClxF) cathode material for SIBs. Density functional theory investigation reveals that Cl doping tunes the localized electronic density and structure in NVPO2F lattice, causing the electron redistribution on vanadium center and dangling anions. Hence, the NVPO2−xClxF cathode exhibits a revised redox behavior of vanadium for Na+ extraction/insertion, increases Na+ diffusion rate, as well as lowers charge transfer resistance. A Na+ storage mechanism of reversible transformations between three phases and V4+/V5+ redox couple for NVPO2−xClxF cathode is verified. The NVPO2−xClxF cathode reveals a high rate capacity of ≈63 mAh g−1 at 30C and great cycle stability over 1000 cycles at 10C. More importantly, outstanding rate property (314 Wh kg−1 at 5850 W kg−1) and cycling capability are obtained for the NVPO2−xClxF//3DC@Se full cell. This study demonstrates a brand‐new strategy to prepare advanced cathode materials for superior SIBs.
Cl‐doped Na3V2(PO4)2O2F (NVPO2−xClxF) cathode material is prepared for the first time via a facile chemical vapor replacing process. The density functional theory investigations verify that the Cl doping tunes the electronic structure and causes the electron redistribution on vanadium center/dangling anions. Therefore, a revised redox behavior of vanadium and increased Na+ diffusivity are achieved, enabling superior rate property.
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.
