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.

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.

Mesoscale interplay among composition heterogeneity,lattice deformation,and redox stratification in single-crystalline layered oxide cathode

Single-crystalline layered oxide materials for lithium-ion batteries are featured by their excellent capacity retention over their polycrystalline counterparts,making them sought-after cathode candidates.Their capacity degradation,however,becomes more severe under high-voltage cycling,hindering many high-energy applications.It has long been speculated that the interplay among composition heterogeneity,lattice deformation,and redox stratification could be a driving force for the performance decay.The underlying mechanism,however,is not well-understood.In this study,we use X-ray microscopy to systematically examine single-crystalline NMC particles at the mesoscale.This technique allows us to capture detailed signals of diffraction,spectroscopy,and fluorescence,offering spatially resolved multimodal insights.Focusing on early high-voltage charging cycles,we uncover heterogeneities in valence states and lattice structures that are inherent rather than caused by electrochemical abuse.These heterogeneities are closely associated with compositional variations within individual particles.Our findings provide useful insights for refining material synthesis and processing for enhanced battery longevity and efficiency.

离子交换法在钠钙硅酸盐玻璃中原位合成银纳米颗粒的研究

采用离子交换结合热处理法,在商用钠钙硅酸盐平板玻璃中原位形成2～7 nm的银纳米颗粒.利用电子探针、X射线吸收近边结构谱、透射电子显微镜和高分辨透射电子显微镜研究了银离子在玻璃中的扩散、还原和生长机理.结果表明:玻璃中同时存在2价和3价铁离子,2价铁离子的存在有利于银离子被还原成中性银原子.银原子在玻璃中成核并生长成纳米颗粒.银纳米颗粒可以在离子交换时形成.提高热处理温度比延长热处理时间更有利于颗粒长大.特别当热处理温度高于玻璃转变温度时,出现Ostwald生长,导致银颗粒迅速长大,密度降低.大部分银纳米颗粒为十四面体单晶,少量为孪晶结构.

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.

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.

Sodium ion storage performance and mechanism in orthorhombic V_(2)O_(5) single-crystalline nanowires

A fundamental understanding of the electrochemical reaction process and mechanism of electrodes is very crucial for developing high-performance electrode materials.In this study,we report the sodium ion storage behavior and mechanism of orthorhombic V_(2)O_(5) single-crystalline nanowires in the voltage window of 1.0–4.0 V(vs.Na/Na+).The single-crystalline nanowires exhibit a large irreversible capacity loss during the first discharge/charge cycle,and then show excellent cycling stability in the following cycles.At a current density of 100 mA g^(−1),the nanowires electrode delivers initial discharge/charge capacity of 217/88 mA h g^(−1),corresponding to a Coulombic efficiency of only 40.5%;after 100 cycles,the electrode remains a reversible discharge capacity of 78 mA h g^(−1) with a fading rate of only 0.09%per cycle compared with the 2nd cycle discharge capacity.The sodium ion storage mechanism was investigated,illustrating that the large irreversible capacity loss in the first cycle can be attributed to the initially formed single-crystalline α′-Nax V_(2)O_(5)(0.02<x<0.88),in which sodium ions cannot be electrochemically extracted and the α′-Na0.88 V_(2)O_(5) can reversibly host and release sodium ions via a single-phase(solid solution)reaction,leading to excellent cycling stability.The Na^(+) diffusion coefficient in α′-Nax V_(2)O_(5) ranges from 10^(−12) to 10^(−11.5) cm^(2) s^(−1) as evaluated by galvanostatic intermittent titration technique(GITT).

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.

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.

Two highly porous single-crystalline zirconium-based metal-organic frameworks

Herein we report two highly porous Zr-based metal-organic frameworks （MOFs, 1 and 2） constructed by the truncated octahedral secondary building unit （SBU） of Zr604（OH）4（CO2）12 and the organic linear ligand of 4,4＇-stilbenedicarboxylic acid （H2sbdc） or 4,4＇-azobenezenedicarboxylic acid （H2abdc）. Both Zr-based MOFs are obtained as single crystals of suitable size for single-crystal X-ray diffraction analysis. Furthermore, these two Zr-based MOFs have been fully characterized by powder X-ray diffraction （PXRD） studies, thermogravimetric analysis （TGA）, infrared spectroscopy （IR） and gas adsorption analysis. In particular, their CO2 gas adsorption behaviors have been investigated and discussed.

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.

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.

The 13-atom encapsulated gold cage clusters

The structure and the magnetic moment of transition metal encapsulated in a Au 12 cage cluster have been studied by using the density functional theory.The results show that all of the transition metal atoms（TMA） can embed into the Au 12 cage and increase the stability of the clusters except Mn.Half of them have the I h or O h symmetry.The curves of binding energy have oscillation characteristics when the extra-nuclear electrons increase;the reason for this may be the interaction between parity changes of extra-nuclear electrons and Au atoms.The curves of highest occupied molecular orbital-lowest unoccupied molecular orbital（HOMO-LUMO） gap also have oscillation characteristics when the extra-nuclear electrons increase.The binding energies of many M@Au 12 clusters are much larger than that of the pure Au 13 cluster,while the gaps of some of them are less than that of Au 13,so maybe Cr@Au 12,Nb@Au 12,and W@Au 12 clusters are most stable in fact.For magnetic calculations,some clusters are quenched totally,but the Au 13 cluster has the largest magnetic moment of 5 μ B.When the number of extra-nuclear electrons of the encapsulated TMA is even,the magnetic moment of relevant M@Au 12 cluster is even,and so are the odd ones.

Sodium carbonate-assisted synthesis of hierarchically porous single-crystalline nanosized zeolites

Hierarchically porous single-crystalline nanosized zeolites as heterogeneous catalysts show great poten- tial in fine chemistry because they offer more rich hierarchically porous channels for the mass transfer and molecular diffusion. However, the synthesis of hierarchically porous nanosized zeolites generally requires the assistance of templates acting as the mesoporogens, which limits its popularity. Herein, we report a one-pot and template-free synthesis of hierarchically porous single-crystalline nanosized zeolite beta only by introducing sodium carbonate in precursor solution. The resulted sample features the extraordinary properties, including the uniform nanocrystal （200-300 nm）, high pore volume （0.65 cm3g 1） and the hierarchical pore-size distribution （e.g., 2-8 and 90-150 nm）. After slicing pro- cessing, it is interestingly found that a large number of interconnected mesopores penetrate throughout whole material, which enables the hierarchically porous nanosized zeolite beta remarkably superior cat- alytic activity than the conventional zeolite beta in condensation of henzaldehyde with ethanol at room temperature. More importantly, this one-pot sodium carbonate-assisted synthetic strategy is highly ver- satile, which has also been successfully developed to synthesize hierarchically porous nanosized single- crystalline zeolites ZSM-5 and TS.

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.

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.