Regulating the electrochemical activity of Fe-Mn-Cu-based layer oxides as cathode materials for high-performance Na-ion battery

Fe-Mn based layer oxides cathode materials have attracted widespread attention as a potential candidate for sodium-ion batteries(SIBs)owing to the earth abundance,cost-effectiveness and acceptable specific capacity.However,the irreversible phase transition often brings rapid capacity decay,which seriously hinders the practical application in large-scale energy storage.Herein,we design a nickel-doped Na_(0.70)Fe_(0.10)Cu_(0.20)Ni_(0.05)Mn_(0.65)O_(2)(NFCNM-0.05)cathode material of SIBs with activated anionic redox reaction,and then inhibit the harmful phase transition.The ex-situ X-ray diffraction patterns demonstrate the NFCNM-0.05 always keeps the P2 phase during the sodiation/desodiation process,indicating a high structure stability.The ex-situ X-ray photoelectron spectroscopy implies the redox reactions between O2-and O-occur in the charging process,which offers extra specific capacity.Thus,the NFCNM-0.05 electrode delivers a high initial discharge capacity of 148 mA h g-1and remains a prominent cycling stability with an excellent capacity retention of 95.9%after 200 cycles at 1 C.In addition,the electrochemical impedance spectroscopy and galvanostatic intermittent titration technique show the NFCNM-0.05 electrode possesses fast ion diffusion ability,which is beneficial for the enhancement of rate performance.Even at 10 C,the NFCNM-0.05 can offer a reversible discharge capacity of 81 mA h g-1.DFT calculation demonstrates the doping of appropriate amount of Ni ions is benefit for the enhancement of the electrochemical performance of the layer oxides.This work provides an effective strategy to enhance the electrochemical performance of Fe-Mn based cathode materials of SIBs.

Redox Controllable Switch of Crystalline Phase and Physical Property in SrVO_x Epitaxial Films

Transition-metal oxides have attracted much attention due to its abundant crystalline phases and intriguing physical properties. However, some of these compounds are difficult to be fabricated directly in film form due to the ease of valence variation of transition-metal elements.In this work, we reveal the reversible structural transition between SrVO3 and Sr2V2O7 films via thermal treatment in oxygen atmosphere or in vacuum. Based on this, Sr2V2O7 epitaxial films are successfully synthesized and studied. Property characterizations show that the semitransparent and metallic SrVO3 could reversibly switch into transparent and insulating Sr2V2O7, implying potential applications in controllable electronic and optical devices.

A smart safe rechargeable zinc ion battery based on sol-gel transition electrolytes

Thermal runaway has been a long-standing safety issue impeding the development of high-energy- density batteries. Physical safety designs such as employing circuit-breakers and fuses to batteries are limited by small operating voltage windows and no resumption of original working condition when it is cooled down. Here we report a smart thermoresponsive polymer electrolyte that can be incorporated inside batteries to prevent thermal runaway via a fast and reversible sol-gel transition, and successfully combine this smart electrolyte with a rechargeable Zn/^-Mn02 battery system. At high temperature, bat- tery operation is inhibited as a result of the increased internal resistance caused by the gelation of liquid electrolyte. After cooling down, the electrolyte is spontaneously reversed to sol state and the electro- chemical performance of the battery is restored. More importantly, sol-gel transition enables the smart battery to experience different charge-discharge rates under various temperature levels, providing a smart and active strategy to achieve dynamic and reversible self-protection.

Ultrahigh quantum efficiency photodetector and ultrafast reversible surface wettability transition of square In2O3 nanowires

Due to a large surface-to-volume ratio, the optoelectronic performance of low- dimensional semiconductor nanostructure-based photodetectors depends in principle on chemisorption/photodesorption at the exposed surface, but practical examples that show such an effect are still unavailable. Some theoretical calculations have predicted that the {001} facets of In2O3 can effectively accumulate photogenerated holes under irradiation, providing a model material to examine whether the facet cutting of nanowires （NWs） can boost their optoelectronic performance. Herein, we present the design and construction of a novel nanowire-based photodetector using square In2O3 NWs with four exposed {001} crystal facets. The photodetector delivers excellent optoelectronic performance with excellent repeatability, fast response speed, high spectral responsivity （Rλ）, and high external quantum efficiency （EQE）. The Rλ and EQE values are as high as 4.8 × 10^6 A/W and 1.46 × 10^9%, respectively, which are larger than those of other popular semiconductor photodetectors. In addition, the square In2O3 NWs show hydrophobic wettability as manifested by a contact angle of 118° and a fast photoinduced reversible switching behavior is observed.

Oxygen vacancy promising highly reversible phase transition in layered cathodes for sodium-ion batteries

Phase transition is common during (de)-intercalating layered sodium oxides, which directly affects the structural stability and electrochemical performance. However, the artificial control of phase transition to achieve advanced sodium-ion batteries is lacking, since the remarkably little is known about the influencing factor relative to the sliding process of transition-metal slabs upon sodium release and uptake of layered oxides. Herein, we for the first time demonstrate the manipulation of oxygen vacancy concentrations in multinary metallic oxides has a significant impact on the reversibility of phase transition, thereby determining the sodium storage performance of cathode materials. Results show that abundant oxygen vacancies intrigue the return of the already slide transition-metal slabs between O_(3) and P_(3) phase transition, in contrast to the few oxygen vacancies and resulted irreversibility. Additionally, the abundant oxygen vacancies enhance the electronic and ionic conductivity of the Na0.9Ni0.3Co0.15Mn0.05Ti0.5O2 electrode, delivering the high initial Coulombic efficiency of 97.1%, large reversible capacity of 112.7 mAh·g−1, superior rate capability upon 100 C and splendid cycling performance over 1,000 cycles. Our findings open up new horizons for artificially manipulating the structural evolution and electrochemical process of layered cathodes, and pave a way in designing advanced sodium-ion batteries.

The genomics of desmoplastic small round cell tumor reveals the deregulation of genes related to DNA damage response, epithelial-mesenchymal transition, and immune response

Background:Desmoplastic small round cell tumor(DSRCT)is a rare,aggressive,and poorly investigated simple sarcoma with a low frequency of genetic deregulation other than an Ewing sarcoma RNA binding protein 1(EWSR1)-Wilm’s tumor suppressor(WT1)translocation.We used whole-exome sequencing to interrogate six consecutive pretreated DSRCTs whose gene expression was previously investigated.Methods:DNA libraries were prepared from formalin-fixed,paraffin-embedded archival tissue specimens following the Agilent SureSelectXT2 target enrichment protocol and sequenced on Illumina NextSeq 500.Raw sequence data were aligned to the reference genome with Burrows-Wheeler Aligner algorithm.Somatic mutations and copy number alterations(CNAs)were identified using MuTect2 and EXCAVATOR2,respectively.Biological functions associated with altered genes were investigated through Ingenuity Pathway Analysis(IPA)software.Results:A total of 137 unique somatic mutations were identified:133 mutated genes were case-specific,and 2 were mutated in two cases but in different positions.Among the 135 mutated genes,27%were related to two biological categories:DNA damage-response(DDR)network that was also identified through IPA and mesenchymal-epithelial reverse transition(MErT)/epithelial-mesenchymal transition(EMT)already demonstrated to be relevant in DSRCT.The mutated genes in the DDR network were involved in various steps of transcription and particularly affected pre-mRNA.Half of these genes encoded RNA-binding proteins or DNA/RNA-binding proteins,which were recently rec-ognized as a new class of DDR players.CNAs in genes/gene families,involved in MErT/EMT and DDR,were recurrent across patients and mostly segregated in the MErT/EMT category.In addition,recurrent gains of regions in chromosome 1 involving many MErT/EMT gene families and loss of one arm or the entire chromosome 6 affecting relevant immune-regulatory genes were recorded.Conclusions:The emerging picture is an extreme inter-tumor heterogeneity,characterized by the concurrent deregulation of the DDR and MErT/EMT dynamic and plastic programs that could favour genomic instability and explain the refractory DSRCT profile.

Thermodynamics of charged black holes in Maxwell-dilaton-massive gravity

Considering the nonminimal coupling of the dilaton field to the massive graviton field in Maxwelldilaton-massive gravity,we obtain a class of analytical solutions of charged black holes,which are neither asymptotically flat nor(A)dS.The calculated thermodynamic quantities,such as mass,temperature,and entropy,verify the validity of the first law of black hole thermodynamics.Moreover,we further investigate the critical behaviors of these black holes in the grand canonical and canonical ensembles and find a novel critical phenomenon never before observed,known as the"reverse"reentrant phase transition with a tricritical point.It implies that the system undergoes a novel"SBH-LBH-SBH"phase transition process and is the reverse of the"LBH-SBH-LBH"process observed in reentrant phase transitions.

Integrated in-memory sensor and computing of artificial vision system based on reversible bonding transition-induced nitrogen-doped carbon quantum dots (N-CQDs)

Carbon quantum dots (CQDs) have been used in memristors due to their attractive optical and electronic properties, which are considered candidates for brain-inspired computing devices. In this work, the performance of CQDs-based memristors is improved by utilizing nitrogen-doping. In contrast, nitrogen-doped CQDs (N-CQDs)-based optoelectronic memristors can be driven with smaller programming voltages (−0.6 to 0.7 V) and exhibit lower powers (78 nW/0.29 µW). The physical mechanism can be attributed to the reversible transition between C–N and C=N with lower binding energy induced by the electric field and the generation of photogenerated carriers by ultraviolet light irradiation, which adjusts the conductivity of the initial N-CQDs to implement resistance switching. Importantly, the convolutional image processing based on various cross kernels is efficiently demonstrated by stable multi-level storage properties. An N-CQDs-based optoelectronic reservoir computing implements impressively high accuracy in both no noise and various noise modes when recognizing the Modified National Institute of Standards and Technology (MNIST) dataset. It illustrates that N-CQDs-based memristors provide a novel strategy for developing artificial vision system with integrated in-memory sensor and computing.

Responsive switchable deep eutectic solvents:A review

Deep eutectic solvents(DESs)have drawn considerable attention as a new type of green solvent since they were reported.Subsequent studies have shown that DESs have the potential to be used as“designable”solvents,which means that the precursors of DESs with different structures and properties can be screened to customize DESs for specific functions.Researchers have found that during the sample preparation process involving DESs,the specific properties of some“smart”DESs can be switched by directing external driving forces,leading to a reversible phase transition of the target solution.These"smart"DESs are called switchable deep eutectic solvents(SDESs).The advent of SDES simplifies the sample pretreatment steps,reduces the use of organic solvents,and makes solvents easy to recycle,which matches the concept of green and sustainable chemistry.Compared with the number of previous experimental studies,the reviews and summaries on SDESs are rare.Therefore,this review made a summary of the concept and research progress of SDESs based on some related works in the past decade,including composition and type,characterization,switching mechanism,etc.It is expected to provide a certain reference and guidance for the subsequent in-depth research of SDESs in the analytical sample pretreatment.

Optimizing strain response in lead-free(Bi_(0.5)Na_(0.5))TiO_(3)-BaTiO_(3)-NaNbO_(3)solid solutions via ferroelectric/(non-)ergodic relaxor phase boundary engineering

Lead-free bismuth sodium titanate(Bi_(0.5)Na_(0.5))TiO_(3)(BNT)and related solid solutions are potential piezoelectric materials for such applications as actuators and transducers if their excellent strain responses and piezoelectric properties can be optimized.In this work,a large strain response of 0.61%is achieved in lead-free(0.94-x%)(Bi_(0.5)Na_(0.5))TiO_(3)-0.06BaTiO_(3)-x%NaNbO_(3)(x=0 e6,BNT-6BT-xNN)ceramics with the composition of x=3.5 in a pseudo-cubic structure.Coexistence of ferroelectric(FE)and relaxor(RE)domain structures is observed in all the unpoled ceramics and the enhanced strain response is believed to be related to the evolution of the ergodic relaxor(ER)and non-ergodic(NR)states thanks to the substitution of antiferroelectric NN.BNT-6BT-3.5NN is a critical composition near the FE/NR/ER phase boundary close to room temperature(RT)and its high strain response arises from a synergistic combination of a reversible electric-field-induced phase transition and an active domain switching in the mixed NR/ER state.This work provides new insights into the dynamic interplay between mesoscopic domains and macroscopic electrical properties in the BNT-based piezoceramics.

Nanofiber-based transparent film with controllable optical transparency adjustment function for versatile bionic applications

As a new favorite in the field of smart materials,smart windows,with visual stimulus sensing functions,have attracted extensive attention for their high transparency,sensitive response to environmental stimulus,and reversible changes in light transmittance.In this paper,the PVA-coPE nanofiber film,which was completely opaque like paper,was used as filling phase and reacted with water-soluble N-vinyl-2-pyrrolidone(NVP)by photopolymerization to produce a flexible transparency polyvinyl pyrrolidone/spraying PVA-co-PE nanofiber films(PVP/SPNFs)composite film.Among them,the small size effect of PVA-coPE nanofibers played a pivotal role in improving the film's transparency.Nevertheless,the PVP's reversible adsorption-desorption behavior of water molecules made its refractive index change dynamically and reversibly,which led to the visual transition of composite film from transparent to opaque just like that of electronic smart windows.Additionally,the reversible transition rate of film's transparency can be effectively regulated by the nanofiber stack structure.This new design of transparency visualization transforms composite film in response to humidity,innovates the electrically controlled smart windows on energy and realizes the effective utilization of natural resources such as water and humidity,which has a great application prospect in the field of flexible optoelectronic devices,intelligent buildings,and smart writing.

Smart Multiple Wetting Control on ZnO Coated Shape Memory Polymer Arrays

Recently,surfaces with intelligent wetting controllability have aroused increased attention.Endowing the surface with stimuli-responsive surface chemistry and tunable surface microstructure can achieve a surface with smart wetting performances.However,almost all existing surfaces only focused on single surface chemistry or micromorphology,thus to achieve smart multiple wetting regulation is still difficult.Herein,we report a ZnO coated shape memory polymer(SMP)surface,and the surface chemistry and micromorphology can be synergistically regulated.ZnO can provide adjustable surface chemistry under UV irradiation,and SMP can offer tunable micromorphology due to its shape memory effect(SME).Based on the combined effect between the above two features,surface wetting performance can be smartly regulated among multiple states.Moreover,due to the excellent controllability of the surface,the application in directional droplet transportation was also demonstrated.This paper offers a new surface with tunability in both surface chemistry and micromorphology,and given the excellent wetting controllability,the surface is believed to be applied in a lot of fields,such as droplet manipulation,fluidic devices and selective catalysis.

A new association state of solutes in nanoconfined aqueous solutions

Recently, we have found a reversible transition between the dispersion and aggregation states of solute molecules in aqueous solutions confined in nanoscale geometry, where solutes exhibit distinct behavior in a new association state from that in the dispersion and aggregation states observed usually in macroscopic systems. However, it remains unknown whether this new association state of solute molecules found in nanoconfined systems would vanish with the system size increasing and approaching the macroscopic scale. Here, we achieve the phase diagram of solute association states by making the analyses of Gibbs free energy of solutes in nanoconfined aqueous solutions in detail. In the phase diagram, we observe a closed regime with a finite system size of nanoconfined aqueous solutions and a solute concentration range, only in which there exists the new association state of solutes with the reversible transition between the aggregation and dispersion states, and there indeed exists an upper limit of the system size for the new association state, around several tens nanometers. These findings regarding the intimate connection between the system size and the solute association behavior provides the comprehensive understanding of the association dynamics of solutes in nanoconfined environment.

Temperature-driven reversible structural transformation and conductivity switching in ultrathin Cu_(9)S_(5)crystals

Two-dimensional(2D)materials with reversible phase transformation are appealing for their rich physics and potential applications in information storage.However,up to now,reversible phase transitions in 2D materials that can be driven by facile nondestructive methods,such as temperature,are still rare.Here,we introduce ultrathin Cu_(9)S_(5)crystals grown by chemical vapor deposition(CVD)as an exemplary case.For the first time,their basic electrical properties were investigated based on Hall measurements,showing a record high hole carrier density of~1022 cm^(-3) among 2D semiconductors.Besides,an unusual and repeatable conductivity switching behavior at~250 K were readily observed in a wide thickness range of CVD-grown Cu_(9)S_(5)(down to 2 unit-cells).Confirmed by in-situ selected area electron diffraction,this unusual behavior can be ascribed to the reversible structural phase transition between the room-temperature hexagonalβphase and low-temperatureβ’phase with a superstructure.Our work provides new insights to understand the physical properties of ultrathin Cu_(9)S_(5)crystals,and brings new blood to the 2D materials family with reversible phase transitions.