New insights into the pre-lithiation kinetics of single-crystalline Ni-rich cathodes for long-life Li-ion batteries

Developing single-crystalline Ni-rich cathodes is an effective strategy to improve the safety and cycle life of Li-ion batteries(LIBs).However,the easy-to-loss of Li and O in high-temperature lithiation results in unsatisfactory ordered layered structure and stoichiometry.Herein,we demonstrate the synthesis of highly-ordered and fully-stoichiometric single-crystalline LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)cathodes by the regulation of pre-lithiation kinetics.The well-balanced pre-lithiation kinetics have been proved to greatly improve the proportion of layered phase in the intermediate by inhibiting the formation of metastable spinel phase,which promoted the rapid transformation of the intermediate into highly-ordered layered SC-NCM83 in the subsequent lithiation process.After coating a layer of Li_(2)O–B_(2)O_(3),the resultant cathodes deliver superior cycling stability with 90.9%capacity retention at 1C after 300 cycles in pouch-type full batteries.The enhancement mechanism has also been clarified.These findings exhibit fundamental insights into the pre-lithiation kinetics process for guiding the synthesis of high-quality singlecrystalline Ni-rich cathodes.

Effect of particle size of single-crystalline hierarchical ZSM-5 on its surface mass transfer in n-heptane catalytic cracking

Single-crystalline hierarchical ZSM-5 zeolites with different particle sizes(namely 100,140,and 200 nm)were successfully prepared by adjusting the amount of tetrapropylammonium hydroxide(TPAOH),and investigated in n-heptane catalytic cracking reaction.Diffusional measurements by zero-length column(ZLC)method showed that the apparent diffusivities of n-heptane decreased with the reduction of particle size,indicating the existence of surface barriers.Moreover,with the decrease of particle size,the additional diffusion path length increased,which meant the influence of surface barriers became more apparent.Despite the change of surface barriers,the intracrystalline diffusion still dominated the overall diffusion.Catalytic performance showed that the zeolite with smaller particle size had better stability.

Controlled Growth of Large-Area Aligned Single-Crystalline Organic Nanoribbon Arrays for Transistors and Light-Emitting Diodes Driving

Organic field-effect transistors(OFETs) based on organic micro-/nanocrystals have been widely reported with charge carrier mobility exceeding 1.0 cm^2V^(-1)s^(-1), demonstrating great potential for high-performance, low-cost organic electronic applications. However, fabrication of large-area organic micro-/nanocrystal arrays with consistent crystal growth direction has posed a significant technical challenge. Here, we describe a solution-processed dip-coating technique to grow large-area, aligned 9,10-bis(phenylethynyl) anthracene(BPEA) and 6,13-bis(triisopropylsilylethynyl) pentacene(TIPSPEN) single-crystalline nanoribbon arrays. The method is scalable to a 5 9 10 cm^2 wafer substrate, with around 60% of the wafer surface covered by aligned crystals. The quality of crystals can be easily controlled by tuning the dip-coating speed. Furthermore, OFETs based on well-aligned BPEA and TIPS-PEN single-crystalline nanoribbons were constructed.By optimizing channel lengths and using appropriate metallic electrodes, the BPEA and TIPS-PEN-based OFETs showed hole mobility exceeding 2.0 cm^2V^(-1)s^(-1)(average mobility 1.2 cm^2V^(-1)s^(-1)) and 3.0 cm^2V^(-1)s^(-1)(average mobility2.0 cm^2V^(-1)s^(-1)), respectively. They both have a high on/off ratio(I_(on)/I_(off))>10~9. The performance can well satisfy the requirements for light-emitting diodes driving.

Low-temperature growth of large-scale,single-crystalline graphene on Ir(111)

Iridium is a promising substrate for self-limiting growth of graphene. However, single-crystalline graphene can only be fabricated over 1120 K. The weak interaction between graphene and Ir makes it challenging to grow graphene with a single orientation at a relatively low temperature. Here, we report the growth of large-scale, single-crystalline graphene on Ir(111) substrate at a temperature as low as 800 K using an oxygen-etching assisted epitaxial growth method. We firstly grow polycrystalline graphene on Ir. The subsequent exposure of oxygen leads to etching of the misaligned domains.Additional growth cycle, in which the leftover aligned domain serves as a nucleation center, results in a large-scale and single-crystalline graphene layer on Ir(111). Low-energy electron diffraction, scanning tunneling microscopy, and Raman spectroscopy experiments confirm the successful growth of large-scale and single-crystalline graphene. In addition, the fabricated single-crystalline graphene is transferred onto a SiO_2/Si substrate. Transport measurements on the transferred graphene show a carrier mobility of about 3300 cm^2·V^(-1)·s^(-1). This work provides a way for the synthesis of large-scale,high-quality graphene on weak-coupled metal substrates.

Electrical Transport Properties of Type-Ⅷ Sn-Based Single-Crystalline Clathrates (Eu/Ba)8Ga16Sn30 Prepared by Ga Flux Method

Single-crystalline samples of Eu/Ba-filled Sn-based type-Ⅷ clathrate are prepared by the Ga flux method with different stoichiometric ratios. The electrical transport properties of the samples are optimized by Eu doping. Results indicate that Eu atoms tend to replace Ba atoms. With the increase of the Eu initial content, the carrier density increases and the carrier mobility decreases, which leads to an increase of the Seebeck coefficient. By contrast, the electrical conductivity decreases. Finally, the sample with Eu initial content of x = 0.75 behaves with excellent electrical properties, which shows a maximal power factor of 1.51 mW·m^-1K^-2 at 480K, and the highest ZT achieved is 0.87 near the temperature of 483K.

Crack-free single-crystalline Co-free Ni-rich LiNi_(0.95)Mn_(0.05)O_(2) layered cathode

The rapid growth in global electric vehicles(EVs)sales has promoted the development of Co-free,Ni-rich layered cathodes for state-of-the-art high energy-density,inexpensive lithium-ion batteries(LIBs).However,progress in their commercial use has been seriously hampered by exasperating performance deterioration and safety concerns.Herein,a robust single-crystalline,Co-free,Ni-rich LiNi_(0.95)Mn_(0.05)O_(2)(SC-NM95)cathode is successfully designed using a molten salt-assisted method,and it exhibits better structural stability and cycling durability than those of polycrystalline LiNi_(0.95)Mn_(0.05)O_(2) (PC-NM95).Notably,the SC-NM95 cathode achieves a high discharge capacity of 218.2 mAh g^(-1),together with a high energy density of 837.3 Wh kg^(-1) at 0.1 C,mainly due to abundant Ni^(2+)/Ni^(3+) redox.It also presents an outstanding capacity retention(84.4%)after 200 cycles at 1 C,because its integrated single-crystalline structure effectively inhibits particle microcracking and surface phase transformation.In contrast,the PC-NM95 cathode suffers from rapid capacity fading owing to the nucleation and propagation of intergranular microcracking during cycling,facilitating aggravated parasitic reactions and rocksalt phase accumulation.This work provides a fundamental strategy for designing high-performance singlecrystalline,Co-free,Ni-rich cathode materials and also represents an important breakthrough in developing high-safe,low-cost,and high-energy LIBs.

Visualizing fast growth of large single-crystalline graphene by tunable isotopic carbon source

The fast growth of large single-crystalline graphene by chemical vapor deposition on Cu foil remains a challenge for industrial-scale applications. To achieve the fast growth of large single-crystalline graphene, understanding the detailed dynamics governing the entire growth process--including nucleation, growth, and coalescence is important; however, these remain unexplored. In this study, by using a pulsed carbon isotope labeling technique in conjunction with micro-Raman spectroscopy identification, we visualized the growth dynamics, such as nucleation, growth, and coalescence, during the fast growth of large single- crystalline graphene domains. By tuning the supply of the carbon source, a growth rate of 320 μm/min and the growth of centimeter-sized graphene single crystals were achieved on Cu foil.

Single-Crystalline Mesoporous Palladium and Palladium-Copper Nanocubes for Highly Efficient Electrochemical CO_(2) Reduction

Mesoporous single crystals have unique potential in catalysis,but remain unexplored owing to the enormous synthetic challenge that they pose.Herein,we report a facile soft-template method to prepare palladium(Pd)and Pd alloy nanocubes with single-crystallinity and abundant mesoporosity.The successful formation of these exotic nanostructures essentially relies on the cointroduction of cetyltrimethylammonium chloride as the surfactant template and extra Cl^(−) ions as the facet-selective capping agent under well controlled experimental conditions.Thanks to their large surface areas and penetrating mesoporous channels,our products exhibit a great performance for electrochemical CO_(2) reduction.The best sample from alloying palladium with copper enables the efficient formate production with high selectivity(90∼100%)over a broad potential range,and great stability even under the working potential as cathodic as −0.5 V versus a reversible hydrogen electrode.These performance metrics are far superior to previous Pd-based materials,and underscore the structural advantages of our products.

Enhanced Supercapacitance with Porous Single-crystalline GaN Electrode

Capacitance is generally determined by the porous microstructure,electron conduction and the synergy effect of active sites in the porous electrode.In this work,we grew centimeter-scale metallic porous GaN single crystals with conductivity up to 18 S/cm at room temperature.The Cu-catecholates(Cu–CAT)nanowire arrays were grown on porous GaN single crystal to form porous single-crystalline electrode with enhanced supercapacitor performance.The Cu–CAT/GaN single crystalline electrode exhibits specific capacitance of 216 F/g and normalized capacitance of 40μF/cm^(2).After 5000 cycles,it retains 80%of its initial capacitance.The porous single-crystalline GaN electrode has high porosity and excellent conductivity showing high surface capacitance.

Effect of crystal morphology of ultrahigh-nickel cathode materials on high temperature electrochemical stability of lithium ion batteries

Higher nickel content endows Ni-rich cathode materials LiNi_(x)Co_yMn_(1-x-y)O_(2)(x>0.6)with higher specific capacity and high energy density,which is regarded as the most promising cathode materials for Li-ion batteries.However,the deterioration of structural stability hinders its practical application,especially under harsh working conditions such as high-temperature cycling.Given these circumstances,it becomes particularly critical to clarify the impact of the crystal morphology on the structure and high-temperature performance as for the ultrahigh-nickel cathodes.Herein,we conducted a comprehensive comparison in terms of microstructure,high-temperature long-cycle phase evolution,and high-temperature electrochemical stability,revealing the differences and the working mechanisms among polycrystalline(PC),single-crystalline(SC)and Al doped SC ultrahigh-nickel materials.The results show that the PC sample suffers a severe irreversible phase transition along with the appearance of microcracks,resulting a serious decay of both average voltage and the energy density.While the Al doped SC sample exhibits superior cycling stability with intact layered structure.In-situ XRD and intraparticle structural evolution characterization reveal that Al doping can significantly alleviate the irreversible phase transition,thus inhibiting microcracks generation and enabling enhanced structure.Specifically,it exhibits excellent cycling performance in pouch-type full-cell with a high capacity retention of 91.8%after 500 cycles at 55℃.This work promotes the fundamental understanding on the correlation between the crystalline morphology and high-temperature electrochemical stability and provides a guide for optimization the Ni-rich cathode materials.

Laser-induced fabrication of highly branched CuS nanocrystals with excellent near-infrared absorption properties

We report on the successful fabrication of highly branched Cu S nanocrystals by laser-induced photochemical reaction.Surprisingly, the single-crystalline nature with preferential alignment of the（107） orientation can be well improved during the moderate growth process. The branch length drastically increases from about 5 nm to 6 μm with an increase of photochemical reaction time（0-40 min）. The absorption spectra of as-prepared Cu S nanodendrites show that localized surface plasmon resonance（LSPR） peaks can be modulated from about 1037 nm to 1700 nm with an increase of branch length. Our results have a promising potential for photodynamic therapy and biological imaging application.

High-quality perovskite MAPbI_3 single crystals for broad-spectrum and rapid response integrate photodetector

Organic–inorganic single-crystalline perovskites have attracted significant attentions due to their exceptional progress in intrinsic properties＇ investigation and applications in photovoltaics and optoelectronics. In this study, the large perovskite CH3NH3PbI3 single crystal with the largest length of 80 mm was prepared through the method of inverse-temperature crystallization. Meanwhile, the mass production of integrate photodetectors have been fabricated on the single-crystalline wafer and the photoresponse performances were investigated. The results show that the single-crystalline photodetectors have broad spectrum response to 900 nm, rapid response speed（〈40 μs） and excellent stability. These findings are of great importance for future promising perovskite single crystalline for integrated photoelectronic application.

Enhancing structure and cycling stability of Ni-rich layered oxide cathodes at elevated temperatures via dual-function surface modification

High-nickel single-crystal layered oxide material has become the most promising cathode material for electric vehicle power battery due to its high energy density.However,this material still suffers from structural degradation during cycling and especially the severe interfacial reactions at elevated temperatures that exacerbate irreversible capacity loss.Here,a simple strategy was used to construct a dualfunction Li_(1.5)Al_(0.5)Ge_(1.5)P_(3)O_(12)(LAGP)protective layer on the surface of the high-nickel single-crystal(SC)cathode material,leading to SC@LAGP material.The strong Al-O bonding effectively inhibits the release of lattice oxygen(O)at elevated temperatures,which is supported by the positive formation energy of O vacancy from first-principal calculations.Besides,theoretical calculations demonstrate that the appropriate amount of Al doping accelerates the electron and Li^(+)transport,and thus reduces the kinetic barriers.In addition,the LAGP protective layer alleviates the stress accumulation during cycling and effectively reduces the erosion of materials from the electrolyte decomposition at elevated temperatures.The obtained SC@LAGP cathode material demonstrates much enhanced cycling stability even at high voltage(4.6 V)and elevated temperature(55℃),with a high capacity retention of 91.3%after 100 cycles.This work reports a simple dual-function coating strategy that simultaneously stabilizes the structure and interface of the single-crystal cathode material,which can be applied to design other cathode materials.

Growth and structural characteristics of metastableβ-In2Se3 thin films on H-terminated Si(111)substrates by molecular beam epitaxy

Epitaxial growth and structural characteristics of metastableβ-In2Se3 thin films on H-terminated Si(111)substrates are studied.The In2Se3 thin films grown below theβ-to-αphase transition temperature(453 K)are characterized to be strainedβ-In2Se3 mixed with significantγ-In2Se3 phases.The pure-phased single-crystallineβ-In2Se3 can be reproducibly achieved by in situ annealing the as-deposited poly-crystalline In2Se3 within the phase equilibrium temperature window ofβ-In2Se3.It is suggeted that the observedγ-to-βphase transition triggered by quite a low annealing temperature should be a rather lowered phase transition barrier of the epitaxy-stabilized In2Se3 thin-film system at a state far from thermodynamic equilibrium.

High-density/efficient surface active sites on modified separators to boost Li-S batteries via atomic Co^(3+)-Se termination

Various and critical electrocatalytic processes are involved during the redox reactions in the Li-S batteries,which extremely depend on the surface structure and chemical state.Recently,single-atom concept unlocks a route to maximize the use of surface-active atoms,however,further increasing the density of active site is still strictly limited by the inherent structure that single-atoms are only highly-dispersed on substrate.Herein,we provide a viewpoint that an elaborate facet design with singlecrystalline structure engineering can harvest high-density surface active sites,which can significantly boost the electrocatalyst performance for excellent Li-S batteries.Specifically,the single-crystal CoSe_(2)(scCS)exhibits three-types of terminated(011)facet,efficiently obtaining the surface with a high-rich Co^(3+)–Se bond termination,in contrast with lots of surface grain boundaries and dangling bonds in polycrystalline CoSe_(2).Surprisingly,the surface active sites concentration can reach more than 69%.As anticipated,it can provide high-density and high-efficient active sites,enormously suppressing the shuttle effect and improving the reaction kinetics via accelerating the conversion and deposition of polysulfides and Li2S.This surface lattice strategy with element terminated mode is a promising approach for designing electrocatalyst effect-based energy system,not merely for Li-S batteries.

Vapor-phase hydrothermal growth of single crystalline NiS2 nanostructure film on carbon fiber cloth for electrocatalytic oxidation of alcohols to ketones and simultaneous H2 evolution

Electrocatalytic synthesis of value-added chemicals is attracting significant research attention owing to its mild reaction conditions, environmental benignity, and potentially scalable application to organic synthetic chemistry. Herein, we report the preparation of a single-crystalline NiS2 nanostructure film of N 50 nm thickness grown directly on a carbon fiber doth （NiSJCFC） by a facile vapor-phase hydrothermal （VPH） method. NiSJCFC as an electrocatalyst exhibits activity for both the oxygen evolution reaction （OER） and the hydrogen evolution reaction （HER） in alkaline media. Furthermore, a series of alcohols （2-propanol, 2-butanol, 2-pentanol, and cyclohexanol） were electrocatalytically converted to the corresponding ketones with high selectivity, efficienc and durability using the NiSJCFC electrode in alkaline media. In the presence of 0.45 M alcohol, a remarkably decreased overpotential （- 150 mV, vs. RHE） at the NiS2/CFC anode compared with that for water oxidation to generate O2, i.e., the OER, in alkaline media leads to significantly improved H2 generation. For instance, the H2 generation rate in the presence of 0.45 M 2-propanol is almost 1.2-times of that obtained for pure water splitting, but in a system that employs an applied voltage at least 280 mV lower than that required for water splitting to achieve the same current density （20 mA-crn-2）. Thus, our results demonstrate the applicability of our bifunctional non-precious-metal electrocatalyst for organic synthesis and simultaneous H2 production.

Unravelling a solution-based formation of single- crystalline kinked wurtzite nanowires： The case of MnSe

The search for a novel strategy to sculpt semiconductor nanowires （NWs） at the atomistic scale is crucial for the development of new paradigms in optics, electronics, and spintronics. Thus far, the fabrication of single-crystalline kinked semiconductor NWs has been achieved mainly through the vapor-liquid-solid growth technique. In this study, we developed a new strategy for sculpting single-crystalline kinked wurtzite （WZ） MnSe NWs by triggering the nonpolar axial-oriented growth, thereby switching--at the atomistic scale---the NW growth orientation along the nonpolar axes in a facile solution-based procedure. This presents substantial challenges owing to the dominant polar c axis growth in the solution-based synthesis of one-dimensional WZ nanocrystals. More significantly, the ability to continuously switch the nonpolar axial-growth orientation allowed us to craft the kinking landscape of types 150°, 120°, 90°, and 60°. A probabilistic analysis of kinked MnSe NWs reveals the correlations of the synergy and interplay between these two sets of nonpolar axial growth-orientation switching, which determine the actual kinked motifs. Furthermore, discriminating the side-facet structures of the kinked NWs significantly strengthened the spatially selected interaction of Au nanoparticles. We envisage that such a facile solution-based strategy can be useful for synthesizing other single-crystalline kinked WZ-type transition-metal dichalcogenide NWs to develop novel functional materials with finely tuned properties.

Ultra-precision Machining of Micro-step Pillar Array Using a Straight-Edge Milling Tool

Ultra-precision machining has been well known as a very precise and effective way to prototype and fabricate different types of components with microstructures.In this paper,an ultra-precision micro-milling method has been presented to produce a micro-step pillar array as an embossing mold for semiconductor application.Theoretical analysis on machining mechanics indicates that work material property,machining strategy,and cutting tool geometry largely afFect machining distortion on the machined microstructure.Experimental investigation has been conducted on micromachining of the micro-step pillar array using different types of cutting tools and work materials.Experimental results demonstrate that the material property,cutting tool edge radius,and cutting force play a significant role in the machined micro-structure accuracy and surface finish,while grain boundary of brass has no significant effect on the micro-milling performance.The best outcome among the tests done is achieved when using brass as work material and cutting with a straight-edge single crystalline diamond tool.The main reasons to achieve this outcome are based on:the brass material having a higher elastic modulus and the diamond tool having a smaller cutting edge radius,which contributes to better machinability of brass.One micro-step pillar array has been successfully obtained with very precise feature and dimensional accuracy using brass work material and single-crystal diamond tool.It is believed that the outcomes of this study would largely benefit the research community and end-users.