One‑Step Gas-Solid‑Phase Diffusion‑Induced Elemental Reaction for Bandgap‑Tunable Cu_(a)Agm_(1)Bim_(2)I_(n)/CuI Thin Film Solar Cells

Lead-free inorganic copper-silver-bismuth-halide materials have attracted more and more attention due to their environmental friendliness,high element abundance,and low cost.Here,we developed a strategy of one-step gas-solid-phase diffusioninduced reaction to fabricate a series of bandgap-tunable Cu_(a)Agm_(1)Bim_(2)I_(n)/CuI bilayer films due to the atomic diffusion effect for the first time.By designing and regulating the sputtered Cu/Ag/Bi metal film thickness,the bandgap of Cu_(a)Agm_(1)Bim_(2)I_(n)/CuI could be reduced from 2.06 to 1.78 eV.Solar cells with the structure of FTO/TiO_(2)/Cu_(a)Agm_(1)Bim_(2)I_(n)/CuI/carbon were constructed,yielding a champion power conversion efficiency of 2.76%,which is the highest reported for this class of materials owing to the bandgap reduction and the peculiar bilayer structure.The current work provides a practical path for developing the next generation of efficient,stable,and environmentally friendly photovoltaic materials.

Unique double-layer solid electrolyte interphase formed with fluorinated ether-based electrolytes for high-voltage lithium metal batteries

Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.

基于CTA颅内动脉瘤形态联合PHASES评分对破裂出血预测研究

目的:分析头颈部计算机断层扫描血管成像(CTA)联合PHASES评分对颅内动脉瘤(IA)破裂出血的预测价值。方法:回顾性分析2021年10月—2023年9月东莞市长安医院诊治的IA患者临床资料,根据IA破裂出血与否分为IA破裂组(n=46)和IA未破裂组(n=44),收集两组临床资料,对比两组患者CTA影像瘤体特征参数和PHASES评分结果。采用受试者工作特征(ROC)曲线分析两者联合预测动脉瘤破裂的效能。结果:IA破裂组高血压、糖尿病发生率及PHASES评分均高于IA未破裂组,差异有统计学意义(P <0.05)。两组病灶位置以颈内动脉(ICA)和大脑中动脉(MCA)为主,但IA破裂组病灶位置在MCA的占比为41.30%,高于IA未破裂组的20.45%,瘤体>7 mm的最多(瘤体7~9.9 mm占65.22%),瘤体形态不规则占58.7%,未破裂组病灶位置在ICA最多(68.18%),瘤体<7 mm的居多(75.00%),瘤体形态规则囊状动脉瘤占93.18%,差异有统计学意义(P <0.05)。CTA瘤体特征参数比较,IA破裂组患者瘤颈宽度、瘤体高度、瘤体长度、动脉瘤最大直径、入射夹角、动脉瘤体颈比等参数均高于IA未破裂组,差异有统计学意义(P <0.05)。CTA瘤体特征参数+PHASES评分联合预测曲线下面积为0.916,高于CTA瘤体特征参数(0.901)和PHASES评分(0.731)。结论:CTA瘤体特征参数+PHASES评分联合预测IA患者破裂出血效能最佳。

In situ construction of a stable composite solid electrolyte interphase for dendrite-free Zn batteries

Building a stable solid electrolyte interphase(SEI)has been regarded to be highly effective for mitigating the dendrite growth and parasitic side reactions of Zn anodes.Herein,a robust inorganic composite SEI layer is in situ constructed by introducing an organic cysteine additive to achieve long lifetime Zn metal batteries.The chemisorbed cysteine derivatives are electrochemically reduced to trigger a local alkaline environment for generating a gradient layered zinc hydroxide based multicomponent interphase.Such a unique interphase is of significant advantage as a corrosion inhibitor and Zn^(2+)modulator to enable reversible plating/stripping chemistry with a reduced desolvation energy barrier.Accordingly,the cells with a thin glass fiber separator(260μm)deliver a prolonged lifespan beyond 2000 h and enhanced Coulombic efficiency of 99.5%over 450 cycles.This work will rationally elaborate in situ construction of a desirable SEI by implanting reductive additives for dendrite-free Zn anodes.

Regulating solid electrolyte interphases on phosphorus/carbon anodes via localized high-concentration electrolytes for potassium-ion batteries

The resourceful and inexpensive red phosphorus has emerged as a promising anode material of potassium-ion batteries(PIBs) for its large theoretical capacities and low redox potentials in the multielectron alloying/dealloying reactions,yet chronically suffering from the huge volume expansion/shrinkage with a sluggish reaction kinetics and an unsatisfactory interfacial stability against volatile electrolytes.Herein,we systematically developed a series of localized high-concentration electrolytes(LHCE) through diluting high-concentration ether electrolytes with a non-solvating fluorinated ether to regulate the formation/evolution of solid electrolyte interphases(SEI) on phosphorus/carbon(P/C) anodes for PIBs.Benefitting from the improved mechanical strength and structural stability of a robust/uniform SEI thin layer derived from a composition-optimized LHCE featured with a unique solvation structure and a superior K+migration capability,the P/C anode with noticeable pseudocapacitive behaviors could achieve a large reversible capacity of 760 mA h g^(-1)at 100 mA g^(-1),a remarkable capacity retention rate of 92.6% over 200 cycles at 800 mA g^(-1),and an exceptional rate capability of 334 mA h g^(-1)at8000 mA g^(-1).Critically,a suppressed reduction of ether solvents with a preferential decomposition of potassium salts in anion-derived interfacial reactions on P/C anode for LHCE could enable a rational construction of an outer organic-rich and inner inorganic-dominant SEI thin film with remarkable mechanical strength/flexibility to buffer huge volume variations and abundant K+diffusion channels to accelerate reaction kinetics.Additionally,the highly reversible/durable full PIBs coupling P/C anodes with annealed organic cathodes further verified an excellent practical applicability of LHCE.This encouraging work on electrolytes regulating SEI formation/evolution would advance the development of P/C anodes for high-performance PIBs.

Anchoring polysulfide with artificial solid electrolyte interphase for dendrite-free and low N/P ratio Li-S batteries

Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and lithium metal consumption caused by polysulfide corrosion.Herein we design a dualfunction PMMA/PPC/LiNO3composite as an artificial solid electrolyte interphase(PMCN-SEI)to protect Li metal anode.This SEI offers multiple sites of C=O for polysulfide anchoring to constrain corrosion of Li metal anode.The lithiated polymer group and Li3N in PMCN-SEI can homogenize lithium-ion deposition behavior to achieve a dendrite-free anode.As a result,the PMCN-SEI protected Li metal anode enables the Li||Li symmetric batteries to maintain over 300 cycles(1300 h)at a capacity of 5 m Ah cm^(-2),corresponding to a cumulative capacity of 3.25 Ah cm^(-2).Moreover,Li-S batteries assembled with 20μm of Li metal anode(N/P=1.67)still deliver an initial capacity of 1166 m A h g-1at 0.5C.Hence,introducing polycarbonate polymer/inorganic composite SEI on Li provides a new solution for achieving the high energy density of Li-S batteries.

Uncovering the solid-phase conversion mechanism via a new range of organosulfur polymer composite cathodes for lithium-sulfur batteries

The sulfur cathodes operating via solid phase conversion of sulfur have natural advantages in suppressing polysulfide dissolution and lowering the electrolyte dosage,and thus realizing significant improvements in both cycle life and energy density.To realize an ideal solid-phase conversion of sulfur,a deep understanding of the regulation path of reaction mechanism and a corresponding intentional material and/or cathode design are highly essential.Herein,via covalently fixing of sulfur onto the triallyl isocyanurate,a series of S-triallyl isocyanurate organosulfur polymer composites(STIs) are developed.Relationship between the structure and the electrochemical conversion behavior of STIs is systematically investigated.It is found that the structure of STIs varies with the synthetic temperature,and correspondingly the electrochemical redox of sulfur can be controlled from conventional "solid-liquid-solid" conversion to the "solid-solid" one.Among the STI series,the STI-5 composite realizes an ideal solid-phase conversion and demonstrates great potential for building a Li-S battery with high-energy density and long-cyclelife:it realizes stable cycling over 1000 cycles in carbonate electrolyte,with a degradation rate of0.053% per cycle;the corresponding pouch cell shows almost no capacity decay for 125 cycles under the conditions of high sulfur loading(4.5 mg cm^(-2)) and lean electrolyte(8 μL mg_s^(-1)).In addition,the tailoring strategy of STI can also apply to other precursors with allyl functional groups to develop new organosulfur polymers for "solid-solid" sulfur cathodes.The vulcanized triallyl phosphate(STP) and triallylamine(STA) both show great lithium storage potential.This strategy successfully develops a new family of organosulfur polymers as cathodes for Li-S batteries via solid-phase conversion of sulfur,and brings insights to the mechanism study in Li-S batteries.

Electrode-compatible fluorine-free multifunctional additive regulating solid electrolyte interphase and solvation structure for high-performance lithium-ion batteries

The rapid development and widespread application of lithium-ion batteries(LIBs) have increased demand for high-safety and high-performance LIBs. Accordingly, various additives have been used in commercial liquid electrolytes to severally adjust the solvation structure of lithium ions, control the components of solid electrolyte interphase, or reduce flammability. While it is highly desirable to develop low-cost multifunctional electrolyte additives integrally that address both safety and performance on LIBs, significant challenges remain. Herein, a novel phosphorus-containing organic small molecule, bis(2-methoxyethyl) methylphosphonate(BMOP), was rationally designed to serve as a fluorine-free and multifunctional additive in commercial electrolytes. This novel electrolyte additive is low-toxicity,high-efficiency, low-cost, and electrode-compatible, which shows the significant improvement to both electrochemical performance and fire safety for LIBs through regulating the electrolyte solvation structure, constructing the stable electrode-electrolyte interphase, and suppressing the electrolyte combustion. This work provides a new avenue for developing safer and high-performance LIBs.

A developed transient gas-liquid-solid flow model with hydrate phase transition for solid fluidization exploitation of marine natural gas hydrate reservoirs

The multiphase flow characteristic is one of the most concerning problems during solid fluidization exploitation of marine natural gas hydrate reservoirs.In this research,a new transient gas-liquid-solid multiphase flow model with hydrate phase transition was developed.Meanwhile,this model considered the coupling relationship among convective heat transfer,hydrate dynamic decomposition,and multi-phase flow.The model can simulate the change of flow pattern from solid-liquid to gas-liquid-solid flow,and describe the distribution character of volume fraction of phase,wellbore temperature and pressure,and hydrate decomposition rate during transportation.The simulation results indicate that the hydrate decomposition region in the wellbore gradually expands,but the hydrate decomposition rate gradually decreases during the solid fluidization exploitation of hydrate.When mining time lasts for 4 h,and the bottom hole pressure decreases by about 0.4 MPa.Increasing NaCl concentration in seawater helps expand hydrate decomposition regions and improves the wellbore hydrate decomposition rate.When the Nacl mass fraction in seawater reaches 15%,it will raise the hydrate decomposition regions to the whole wellbore.In addition,the higher the wellhead backpressure,the lower the decomposition area and decomposition rate of hydrate in the wellbore.When wellhead backpressure reaches 2 MPa,the volume fraction of gas near the wellhead will reduce to about 12%.This work is expected to provide a theoretical basis for the development of marine hydrate reservoirs.

Deciphering the potassium storage phase conversion mechanism of phosphorus by combined solid-state NMR spectroscopy and density functional theory calculations

Phosphorus is the potential anode material for emerging potassium-ion batteries(PIBs)owing to the highest specific capacity and relatively low operation plateau.However,the reversible delivered capacities of phosphorus-based anodes,in reality,are far from the theoretical capacity corresponding to the formation of K3P alloy.And,their underlying potassium storage mechanisms remain poorly understood.To address this issue,for the first time,we perform high-resolution solid-state31P NMR combined with XRD measurements,and density functional theory calculations to yield a systemic quantitative understanding of(de)potassiation reaction mechanism of phosphorus anode.We explicitly reveal a previously unknown asymmetrical nanocrystalline-to-amorphous transition process via rP←→(K_(3)P_(11),K_(3)P_(7),beta-K_(4)P_(6))←→(alpha-K4P6)←→(K_(1-x)P,KP,K_(4-x)P3,K_(1+x)P)←→(amorphous K4P3,amorphous K3P)that are proceed along with the electrochemical potassiation/depotassiation processes.Additionally,the corresponding KP alloys intermediates,such as the amorphous phases of K_(4)P_(3),K_(3)P,and the nonstoichiometric phases of“K_(1-x)P”,“K_(1+x)P”,“K_(4-x)P_(3)”are experimentally detected,which indicating various complicated K-P alloy species are coexisted and evolved with the sluggish electrochemical reaction kinetics,resulting in lower capacity of phosphorus-based anodes.Our findings offer some insights into the specific multi-phase evolution mechanism of alloying anodes that may be generally involved in conversion-type electrode materials for PIBs.

Unraveling the heterogeneity of solid electrolyte interphase kinetically affecting lithium electrodeposition on lithium metal anode

The stability and uniformity of solid electrolyte interphase(SEI)are critical for clarifying the origin of capacity fade and safety issues for lithium metal anodes(LMA).However,understanding the interplay of SEI heterogeneity and Li electrodeposition is limited by the coupling of complex electrochemistry and mechanics processes.Herein,the correlation between the SEI failure behavior and Li deposition morphology is investigated through a quantitative electrochemical-mechanical model.The local deformation and stress of SEI during Li electrodeposition identify that the heterogeneous interface between different components first fails.Compared with the well-known mechanical strength,component uniformity plays the most important role in the initial SEI failure and uneven Li deposition,and a relative component uniformity(p>0.01)represents a proper balance to ensure the stability of the naturally heterogeneous SEI.Furthermore,the component regulation of SEI via the designed electrolyte experimentally demonstrates that improving component uniformity benefits SEI stability and the uniform Li electrodeposition for LMA,thereby increasing the capacity by~20%after 300 cycles.These fundamental understandings and proposed strategy can be not only used to guide the SEI optimization via the electrolyte regulation,but also extended to the rational designs of artificial SEI for high-performance LMA.

Analysis on phase selection and microstructure evolution in directionally solidified Zn-Al-Mg-Ce alloy

In the process of hot-dip Zn-Al-Mg alloy coating,the plating solution dissipates heat in the direction perpendicular to the steel plate,which is considered to be a process of directional solidification.To understand the relationship between microstructure and cooling rate of Zn-Al-Mg alloys,both the phase constitution and microstructure characteristic length scales of Zn-9.5Al-3Mg-0.01Ce(wt.%)alloy were investigated by the directional solidification experiments at different growth velocities(V=40,80,160,250μm·s^(-1)).The experimental results show that the microstructure of directionally solidified Zn-9.5Al-3Mg-0.01Ce alloy is composed of primary Al dendrites and(Zn-Al-Mg2Zn11)ternary eutectics at the growth velocities ranging from 40 to 250μm·s^(-1).The primary Al dendrites are aligned regularly along the growth direction,accompanied with obvious secondary dendrites.The relationship between the microstructure length scale and the thermal parameters of solidification is obtained:λ1=374.66V-0.383,andλ2=167.5V-0.563(λ1is the primary dendrite arm spacing,andλ2 is the secondary dendrit arm spacing).In addition,through the interface response function(IRF)and the nucleation and constitutional undercooling(NCU),the phase selection of Zn-9.5Al-3Mg-0.01Ce is obtained:(Zn+Al+Mg2Zn11)ternary eutectics in the Zn-9.5Al-3Mg-0.01Ce alloy will be replaced by ternary eutectics(Zn+Al+MgZn2)when the growth rate is lower than 7.53μm·s^(-1).

Solid-liquid phase equilibrium for the system ammonium polyphosphate-urea ammonium nitrate-potassium chloride-water at 273.2 K

Based on the dynamic method,a quaternary system of ammonium polyphosphate (APP)-urea ammonium nitrate (UAN,CO(NH_(2))_(2)-NH_(4)NO_(3))-potassium chloride (KCl)-H_(2)O and its subsystems (APP-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O,KCl-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O and APP-KCl-H_(2)O) were systematically investigated at the temperature of 273.2 K.Each ternary phase diagram contains one invariant point and three crystallization regions.The crystallization regions are:(1)(NH_(4))_(3)HP_(2)O_(7),(NH_(4))_(4)P_(2)O_(7)and ((NH_(4))_(3)HP_(2)O_(7)+(NH_(4))_(4)P_(2)O_(7)) for APP-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O diagram;(2) KCl,KNO_(3)and(KCl+KNO_(3)) for KCl-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O diagram and (3)(NH_(4))_(3)HP_(2)O_(7),KCl and((NH_(4))_(3)HP_(2)O_(7)+KCl) for APP-KCl-H_(2)O diagram.The quaternary phase diagram of APP-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-KCl-H_(2)O has no quaternary invariant point but includes four solid phase crystallization regions,i.e.,(NH_(4))_(3)HP_(2)O_(7),(NH_(4))_(4)P_(2)O_(7),KNO_(3)and KCl,in which the KNO_(3)region occupies the largest area.The maximum total nutrient content (N+P_(2)O_(5)+K_(2)O) existing as ionic forms in the APP-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O,KCl-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O,APP-KCl-H_(2)O and quaternary systems is 44.70%,32.86%,45.56%and 46.23%(mass),respectively,indicating that the maximum nutrient content can be reached using raw materials of the corresponding systems to prepare liquid fertilizer.In the quaternary system,the content of NH_(4)~+-N ascends with the increase of the total nutrient content,while the contents of NO_(3)^(-)-N and CO(NH_(2))_(2)-N increase with elevated total N.This work can help optimize the operating parameters for the production,storage and transportation of liquid fertilizers.

Moisture-Induced Non-Equilibrium Phase Segregation in Triple Cation Mixed Halide Perovskite Monitored by In Situ Characterization Techniques and Solid-State NMR

Environmental stability is a major bottleneck of perovskite solar cells.Only a handful of studies are investigating the effect of moisture on the structural degradation of the absorber.They mostly rely on ex situ experiments and on completely degraded samples,which restrict the assessment on initial and final stage.By combining in situ X-ray diffraction under controlled 85%relative humidity,and live observations of the water-induced degradation using liquid-cell transmission electron microscopy,we reveal two competitive degradation paths leading on one hand to the decomposition of state-of-theart mixed cation/anion(Cs_(0.05)(MA_(0.17)FA_(0.83))_(0.95)Pb(Br_(0.17)I_(0.83))_(3)(CsMAFA)into PbI_(2) through a dissolution/recrystallization mechanism and,on the other hand,to a non-equilibrium phase segregation leading to CsPb_(2)Br_(5) and a Cesium-poor/iodide-rich Cs_(0.05)-x(MA_(0.17)FA_(0.83))_(0.95)Pb(Br_(0.17-2y)I_(0.83)+2y)_(3) perovskite.This degradation mechanism is corroborated at atomic-scale resolution through solid-state ^(1)H and ^(133)Cs NMR analysis.Exposure to moisture leads to a film containing important heterogeneities in terms of morphology,photoluminescence intensities,and lifetimes.Our results provide new insights and consensus that complex perovskite compositions,though very performant as champion devices,are comparatively metastable,a trait that limits the chances to achieve long-term stability.

In situ observation of the phase transformation kinetics of bismuth during shock release

A time-resolved x-ray diffraction technique is employed to monitor the structural transformation of laser-shocked bismuth.Results reveal a retarded transformation from the shock-induced Bi-Ⅴphase to a metastable Bi-Ⅳphase during the shock release,instead of the thermodynamically stable Bi-Ⅲphase.The emergence of the metastable Bi-Ⅳphase is understood by the competitive interplay between two transformation pathways towards the Bi-Ⅳand Bi-Ⅲ,respectively.The former is more rapid than the latter because the Bi-Ⅴto B-Ⅳtransformation is driven by interaction between the closest atoms while the Bi-Ⅴto B-Ⅲtransformation requires interaction between the second-closest atoms.The nucleation time for the Bi-Ⅴto Bi-Ⅳtransformation is determined to be 5.1±0.9 ns according to a classical nucleation model.This observation demonstrates the importance of the formation of the transient metastable phases,which can change the phase transformation pathway in a dynamic process.

Data-driven optimization study of the multi-relaxation-time lattice Boltzmann method for solid-liquid phase change

Sharp phase interfaces and accurate temperature distributions are important criteria in the simulation of solid-liquid phase changes.The multi-relaxation-time lattice Boltzmann method(MRT-LBM)shows great numerical performance during simulation;however,the value method of the relaxation parameters needs to be specified.Therefore,in this study,a random forest(RF)model is used to discriminate the importance of different relaxation parameters to the convergence,and a support vector machine(SVM)is used to explore the decision boundary of the convergent samples in each dimensional model.The results show that the convergence of the samples is consistent with the sign of the decision number,and two types of the numerical deviations appear,i.e.,the phase mushy zone and the non-physical heat transfer.The relaxation parameters chosen on the decision boundary can further suppress the numerical bias and improve numerical accuracy.

Influence of Omega 3 Fatty Acid Supplementation on Phase Angle Values of People Living with HIV/AIDS with Lipodystrophy Secondary to Antiretroviral Therapy: A Randomized Clinical Trial

Objective: The measurement of phase angles is an important monitoring parameter and supplementation with omega-3 could promote benefits by modulating the electrical potential of membranes and increasing body cell mass. This study aimed to evaluate the effectiveness of omega-3 fatty acid supplementation on the phase angle of people living with HIV/AIDS. Methods: In this study, 63 individuals of all genders who were undergoing outpatient follow-up and showed lipodystrophy due to highly active antiretroviral therapy were analyzed. Our sample consisted of two groups, one that received supplementation containing 2550 mg of omega-3/day (1080 mg of eicosapentaenoic acid and 720 mg of docosahexaenoic acid) for three months (n = 32) and another that underwent nutrition guidance (n = 31). Phase angle and body cell mass were assessed for both groups and compared at the beginning of research (T0) and after our intervention (T1) for each group separately. Results: Phase angle averaged 6.45° ± 1.06 SD. The comparison between T0 and T1 showed a significant increase in phase angle and body cell mass, whereas the guidance group showed a decrease in body cell mass at T1 in relation to T0, with a significant p-value. Variance in phase angle between moments showed significant values between T0 and T1 in the supplementation group for all genders. Conclusion: Omega-3 positively modulated patients phase angle and body cell mass, but we emphasize the need for other studies that can solidify knowledge about supplementation dosage and intervention time.

Phase-engineering modulation of Mn-based oxide cathode for constructing super-stable sodium storage

The Mn-based oxide cathode with enriched crystal phase structure and component diversity can provide the excellent chemistry structure for Na-ion batteries.Nevertheless,the broad application prospect is obstructed by the sluggish Na^(+)kinetics and the phase transitions upon cycling.Herein,we establish the thermodynamically stable phase diagram of various Mn-based oxide composites precisely controlled by sodium content tailoring strategy coupling with co-doping and solid-state reaction.The chemical environment of the P2/P'3 and P2/P3 biphasic composites indicate that the charge compensation mechanism stems from the cooperative contribution of anions and cations.Benefiting from the no phase transition to scavenge the structure strain,P2/P'3 electrode can deliver long cycling stability(capacity retention of 73.8%after 1000 cycles at 10 C)and outstanding rate properties(the discharge capacity of 84.08 mA h g^(-1)at 20 C)than P2/P3 electrode.Furthermore,the DFT calculation demonstrates that the introducing novel P'3 phase can significantly regulate the Na^(+)reaction dynamics and modify the local electron configuration of Mn.The effective phase engineering can provide a reference for designing other high-performance electrode materials for Na-ion batteries.

In-Situ Atomic-Scale Observation of Brownmillerite to Ruddlesden-Popper Phase Transition Tuned by Epitaxial Strain in Cobaltites

Phase transitions involving oxygen ion extraction within the framework of the crystallographic relevance have been widely exploited for sake of superconductivity,ferromagnetism,and ion conductivity in perovskiterelated oxides.However,atomic-scale pathways of phase transitions and ion extraction threshold are inadequately understood.Here we investigate the atomic structure evolution of LaCoO_(3) films upon oxygen extraction and subsequent Co migration,focusing on the key role of epitaxial strain.The brownmillerite to Ruddlesden-Popper phase transitions are discovered to stabilize at distinct crystal orientations in compressive-and tensile-strained cobaltites,which could be attributed to in-plane and out-of-plane Ruddlesden-Popper stacking faults,respectively.A two-stage process from exterior to interior phase transition is evidenced in compressive-strained LaCoO_(2.5),while a single-step nucleation process leaving bottom layer unchanged in tensile-strained situation.Strain analyses reveal that the former process is initiated by an expansion in Co layer at boundary,whereas the latter one is associated with an edge dislocation combined with antiphase boundary.These findings provide a chemomechanical perspective on the structure regulation of perovskite oxides and enrich insights into strain-dependent phase diagram in epitaxial oxides films.

Solid Bi_(2)O_(3)-derived nanostructured metallic bismuth with high formate selectivity for the electrocatalytic reduction of CO_(2)

CO_(2) electrochemical reduction(CO_(2)ER)is an important research area for carbon neutralization.However,available catalysts for CO_(2) reduction are still characterized by limited stability and activity.Recently,metallic bismuth(Bi)has emerged as a promising catalyst for CO_(2) ER.Herein,we report the solid cathode electroreduction of commercial micronized Bi2O3as a straightforward approach for the preparation of nanostructured Bi.At-1.1 V versus reversible hydrogen electrode in a KHCO3aqueous electrolyte,the resulting nanostructure Bi delivers a formate current density of~40 mA·cm^(-2) with a current efficiency of~86%,and the formate selectivity reaches97.6% at-0.78 V.Using nanosized Bi2O3as the precursor can further reduce the primary particle sizes of the resulting Bi,leading to a significantly increased formate selectivity at relatively low overpotentials.The high catalytic activity of nanostructured Bi is attributable to the ultrafine and interconnected Bi nanoparticles in the nanoporous structure,which exposes abundant active sites for CO_(2) electrocatalytic reduction.