Interconnected carbon nanocapsules with high N/S co-doping as stable and high-capacity potassium-ion battery anode

Carbonaceous materials have drawn much attention in potassium-ion batteries (PIBs) due to their low price and superior physicochemical properties. However, the application of carbonaceous materials in PIB anodes is hindered by sluggish kinetics and large volume expansion. Herein, N/S co-doped carbon nanocapsule (NSCN) is constructed for superior K+ storage. The NSCN possesses 3D nanocapsule framework with abundant meso/macropores, which guarantees structural robustness and accelerates ions/electrons transportation. The high-level N/S co-doping in carbon matrix not only generates ample defects and active sites for K+ adsorption, but also expands interlayer distance for facile K+ intercalation/deintercalation. As a result, the NSCN electrode delivers a high reversible capacity (408 mAh g^(−1) at 0.05 A g^(−1)), outstanding rate capability (149 mAh g^(−1) at 5 A g^(−1)) and favorable cycle stability (150m Ah g^(−1) at 2 A g^(−1) after 2000 cycles). Ex situ TEM, Raman and XPS measurements demonstrate the excellent stability and reversibility of NSCN electrode during potassiation/depotassiation process. This work provides inspiration for the optimization of energy storage materials by structure and doping engineering.

Vacancy defect MoSeTe embedded in N and F co-doped carbon skeleton for high performance sodium ion batteries and hybrid capacitors

Sodium-ion batteries(SIBs) and hybrid capacitors(SIHCs) have garnered significant attention in energy storage due to their inherent advantages,including high energy density,cost-effectiveness,and enhanced safety.However,developing high-performance anode materials to improve sodium storage performa nce still remains a major challenge.Here,a facile one-pot method has been developed to fabricate a hybrid of MoSeTe nanosheets implanted within the N,F co-doped honeycomb carbon skeleton(MoSeTe/N,F@C).Experimental results demonstrate that the incorporation of large-sized Te atoms into MoSeTe nanosheets enlarges the layer spacing and creates abundant anion vacancies,which effectively facilitate the insertion/extraction of Na^(+) and provide numerous ion adsorption sites for rapid surface capacitive behavior.Additionally,the heteroatoms N,F co-doped honeycomb carbon skeleton with a highly conductive network can restrain the volume expansion and boost reaction kinetics within the electrode.As anticipated,the MoSeTe/N,F@C anode exhibits high reversible capacities along with exceptional cycle stability.When coupled with Na_(3)V_(2)(PO_(4))_(3)@C(NVPF@C) to form SIB full cells,the anode delivers a reversible specific capacity of 126 mA h g^(-1) after 100 cycles at 0.1 A g^(-1).Furthermore,when combined with AC to form SIHC full cells,the anode demonstrates excellent cycling stability with a reversible specific capacity of50 mA h g^(-1) keeping over 3700 cycles at 1.0 A g^(-1).In situ XRD,ex situ TEM characterization,and theoretical calculations(DFT) further confirm the reversibility of sodium storage in MoSeTe/N,F@C anode materials during electrochemical reactions,highlighting their potential for widespread practical application.This work provides new insights into the promising utilization of advanced transition metal dichalcogenides as anode materials for Na^(+)-based energy storage devices.

Integration of pore structure modulation and B,N co-doping for enhanced capacitance deionization of biomass-derived carbon

Biomass-derived carbon has demonstrated great potentials as advanced electrode for capacitive deionization(CDI),owing to good electroconductivity,easy availability,intrinsic pores/channels.However,conventional simple pyrolysis of biomass always generates inadequate porosity with limited surface area.Moreover,biomass-derived carbon also suffers from poor wettability and single physical adsorption of ions,resulting in limited desalination performance.Herein,pore structure optimization and element co-doping are integrated on banana peels(BP)-derived carbon to construct hierarchically porous and B,N co-doped carbon with large ions-accessible surface area.A unique expansionactivation(EA)strategy is proposed to modulate the porosity and specific surface area of carbon.Furthermore,B,N co-doping could increase the ions-accessible sites with improved hydrophilicity,and promote ions adsorption.Benefitting from the synergistic effect of hierarchical porosity and B,N co-doping,the resultant electrode manifest enhanced CDI performance for NaCl with large desalination capacity(29.5 mg g^(-1)),high salt adsorption rate(6.2 mg g^(-1)min^(-1)),and versatile adsorption ability for other salts.Density functional theory reveals the enhanced deionization mechanism by pore and B,N co-doping.This work proposes a facile EA strategy for pore structure modulation of biomass-derived carbon,and demonstrates great potentials of integrating pore and heteroatoms-doping on constructing high-performance CDI electrode.

高压管汇材料疲劳性能测试及P-S-N模型曲线的拟合

高压管汇作为压裂设备中的主要易损件之一,其失效危害较大。它的失效原因主要是疲劳、冲蚀、腐蚀或者材料缺陷引起的刺漏和爆裂,其中尤以疲劳失效最不可预估。目前,对于高压管汇材料的疲劳性能研究不够深入,为解决高压管汇材料疲劳寿命的准确描述问题,以某国产高压管汇材料为例,进行了一系列疲劳试验,并基于试验数据,采用多种分布模型和不同S-N模型进行拟合分析,得出综合评价拟合能力最强的P-S-N模型。结果表明,该材料在中长疲劳寿命区,Weibull三参数模型在7级应力水平下综合评价能力最好;在存活率分别为50%、90%、99%、99.9%时,指数S-N模型的拟合系数均大于0.98,拟合能力最好。得出的P-S-N模型曲线可以为高压管汇的疲劳寿命以及安全设计提供依据。

基于断裂力学的腐蚀钢丝疲劳S-N曲线研究

高强冷拔钢丝因其优异的力学性能被广泛应用于缆索承重结构,服役过程中钢丝腐蚀与断裂威胁着结构安全。钢丝腐蚀后表面的蚀坑因应力集中效应易产生疲劳裂纹,因此腐蚀钢丝剩余疲劳寿命主要取决于裂纹的扩展阶段,且裂纹扩展受到腐蚀程度(初始损伤)的显著影响。精确表征腐蚀程度并准确评估服役期钢丝腐蚀后的剩余寿命,仍是亟待解决的维修难题。首先采用蚀坑最大深度表征钢丝腐蚀程度,以应力强度因子幅作为裂纹扩展驱动力指标,基于断裂力学的Paris公式建立受拉钢丝裂纹扩展理论模型,进而推导腐蚀钢丝的疲劳S-N曲线。大量既有的腐蚀钢丝疲劳试验结果与理论预测值的比较验证了所提理论模型及疲劳S-N曲线的合理性和有效性。含多个蚀坑的钢丝裂纹扩展有限元模拟表明,等效单裂纹适用于多腐蚀坑钢丝疲劳寿命的简化分析。参数分析表明,蚀坑深度和腐蚀环境是腐蚀钢丝疲劳强度的关键影响因素,而应力比和疲劳加载频率影响较小,所提出的S-N曲线在钢丝常规服役条件下适用于评估其剩余寿命,可得到合理的预测结果。基于断裂力学所提的理论方法和疲劳S-N曲线可为腐蚀钢丝的疲劳强度和寿命评估提供参考。

温度对UNS N08825合金在高含H_(2)S环境中耐腐蚀性能的影响

在不同温度(80,90,110,132℃)、高压、高含H2S和高含氯离子环境中对UNS N08825合金进行了72 h浸泡和电化学腐蚀试验,研究了温度对合金耐腐蚀性能的影响,分析了其影响机理。结果表明:在80℃下试验合金几乎不发生腐蚀,90,110,132℃下合金表面出现黑色腐蚀产物,并且110,132℃下的腐蚀产物增多且呈疏松多孔特征;随着温度升高,合金表面的点蚀坑数量增多且深度增加,最大点蚀速率和均匀腐蚀速率均增大;随着温度升高,试验合金的自腐蚀电位、电荷转移电阻和钝化膜电阻减小,自腐蚀电流密度增大。当温度低于90℃时,合金表面钝化膜均匀致密,点蚀敏感性低,具有较好的耐腐蚀性能;当温度不低于90℃时,元素硫的水解加剧,合金表面钝化膜发生破坏,点蚀更易发生,耐腐蚀性能变差。

采用两步炭化法和熔盐模板法制备N、S共掺杂煤基硬炭及共储钠性能

硬炭因资源丰富、结构稳定及安全性高等优势,已成为钠离子电池常用阳极材料。其中,煤基衍生硬炭受到了广泛的关注。本工作以长焰煤为碳源,硫脲为氮硫源,NaCl为模板,通过两步炭化工艺和杂原子掺杂相结合的方法合成了N和S共掺杂的煤基硬炭(NSPC1200)。两步炭化过程在调节碳微晶结构和扩大层间距方面发挥了重要的作用。N和S的共掺杂调节了炭材料的电子结构,赋予其更多的活性位点;此外,引入NaCl作为模板有助于孔结构的构建,有利于电极和电解质之间的接触,从而实现Na+和电子的有效传输。在协同作用下,样品NSPC1200表现出优异的储钠能力,在20 mA g^(−1)电流密度下呈现314.2 mAh g^(−1)的可逆容量。即使在100 mA g^(−1)下循环200次,仍保持224.4 mAh g^(−1)的比容量。这项工作成功实现了策略性调整煤基炭材料微观结构的目标,最终获得了具有优异的电化学性能的硬炭阳极。

N,S-CQDs/Mn_(0.5)Cd_(0.5)S的制备及光催化产氢性能

采用水热法制备了氮、硫共掺杂碳量子点(N,S-CQDs),并用超声辅助法合成了N,S-CQDs修饰的Mn_(0.5)Cd_(0.5)S(MCS)复合光催化材料.研究表明,在模拟太阳光照射下,质量分数为1%的N,S-CQDs/MCS的光催化产氢速率显著提高,为34159.25μmol/(g·h),是MCS的1.63倍,是质量分数为1%的CQDs/MCS的1.14倍.此复合物光催化产氢性能的提高主要归因于N,S-CQDs优异的电子迁移能力以及MCS与N,S-CQDs之间的紧密接触.

基于N掺杂Ti_(3)C_(2)MXene量子点的荧光探针用于Hg2+和S2-的传感检测

基于N掺杂Ti_(3)C_(2) MXene量子点(N-Ti_(3)C_(2) MQDs)荧光探针和配位相互作用,构建了一种检测Hg^(2+)和S^(2-)的“开-关-开”型荧光传感新方法.研究发现,制备的N-Ti_(3)C_(2) MQDs发射蓝色荧光(λem=440 nm),荧光量子产率为15.7%.Hg^(2+)与N-Ti_(3)C_(2) MQDs表面的—NH2,—COOH,—OH等官能团产生选择性配位作用,导致N-Ti_(3)C_(2) MQDs体系荧光猝灭.当加入S^(2-)后,由于S^(2-)与Hg^(2+)之间强的结合力,形成HgS沉淀,从而使N-Ti_(3)C_(2) MQDs体系荧光恢复.基于该原理,构建了一种“开-关-开”型荧光传感方法,实现了对Hg^(2+)和S^(2-)的定量检测.N-Ti_(3)C_(2) MQDs探针的荧光强度与Hg^(2+)浓度在0.02~200μmol/L范围内呈良好线性关系,检出限为10 nmol/L(S/N=3);与S^(2-)浓度在0.07~150μmol/L范围内呈良好线性关系,检出限为30 nmol/L(S/N=3).该方法具有成本低、操作简单、灵敏度高和选择性好等特点,并可用于水样中Hg^(2+)和S^(2-)的检测.

3.5%NaCl环境中S32205双相不锈钢与N09925镍基合金的钝化膜特征及耐蚀性

采用莫特肖特基(Mott-Schottky)分析方法、电化学阻抗谱(EIS)和X射线光电子能谱(XPS)等,对比研究了S32205双相不锈钢和N09925镍基合金在3.5%NaCl溶液中的钝化膜特征和耐蚀性。结果表明:N09925镍基合金表面钝化膜的缺陷密度低于S32205双相不锈钢,两种材料表面的钝化膜中均存在Fe和Cr元素富集,主要成分为Cr和Fe的氧化物和氢氧化物;S32205双相不锈钢表面钝化膜中含有少量金属Ni,N09925镍基合金表面钝化膜中Ni含量较高,还含有Ni的氧化物和氢氧化物;N09925镍基合金的阻抗值更高,其膜层电阻和电荷传递电阻均高于S32205双相不锈钢,N09925镍基合金表面钝化膜的保护性高于S32205双相不锈钢。

基于S-N曲线的汽车波纹管位移循环载荷寿命研究

建立了汽车波纹管有限元模型,研究了位移循环载荷对汽车波纹管寿命的影响规律,探明了汽车波纹管不同结构参数与等效应力、应变和疲劳寿命之间的关系,并通过正交试验优化了波纹管结构参数。分析了疲劳失效后309S不锈钢汽车波纹管微观组织。结果表明:随着位移循环载荷增大,波纹管疲劳寿命降低,疲劳寿命有限元结果和试验结果误差小于8.8%。增大波高、波距、波宽及减小壁厚有利于提高波纹管疲劳寿命,通过正交试验优化,等效应力由670.5 MPa减小到582.3 MPa,疲劳寿命由80060次增加到241450次。在水涨成形阶段,由于冷变形产生了部分马氏体,位移循环载荷作用下波纹管断裂处硬度接近200 HV,波峰处有明显的裂纹,其内部存在疲劳特征。

Tuning interface mechanism of FeCo alloy embedded N,S-codoped carbon substrate for rechargeable Zn-air battery

The interface mechanism between catalyst and carbon substrate has been the focus of research.In this paper,the FeCo alloy embedded N,S co-doped carbon substrate bifunctional catalyst(FeCo/S-NC)is obtained by a simple one-step pyrolysis strategy.The experimental results and density functional theory(DFT)calculation show that the formation of FeCo alloy is conducive to promoting electron transfer,and the introduction of S atom can enhance the interaction between FeCo alloy and carbon substrate,thus inhibiting the migration and agglomeration of particles on the surface of carbon material.The FeCo/SNC catalysts show outstanding performance for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).FeCo/S-NC shows a high half-wave potential(E_(1/2)=0.8823 V)for ORR and a low overpotential at 10 mA cm^(-2)(E_(j=10)=299 mV)for OER.In addition,compared with Pt/C+RuO_(2) assembled Zn-air battery(ZAB),the FeCo/S-NC assembled ZAB exhibits a larger power density(198.8 mW cm^(-2)),a higher specific capacity(786.1 mA h g_(zn)~(-1)),and ultra-stable cycle performance.These results confirm that the optimized composition and the interfacial interaction between catalyst and carbon substrate synergistically enhance the electrochemical performance.

Ultralong nitrogen/sulfur Co-doped carbon nano-hollowsphere chains with encapsulated cobalt nanoparticles for highly efficient oxygen electrocatalysis

The development of simple and effective strategies to prepare electrocatalysts,which possess unique and stable structures comprised of metal/nonmetallic atoms for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),is currently an urgent issue.Herein,an efficient bifunctional electrocatalyst featured by ultralong N,S-doped carbon nano-hollow-sphere chains about 1300 nm with encapsulated Co nanoparticles(Co-CNHSCs)is developed.The multifunctional catalytic properties of Co together with the heteroatom-induced charge redistribution(i.e.,modulating the electronic structure of the active site)result in superior catalytic activities toward OER and ORR in alkaline media.The optimized catalyst Co-CNHSC-3 displays an outstanding electrocatalytic ability for ORR and OER,a high specific capacity of 1023.6 mAh gZn^(-1),and excellent reversibility after 80 h at 10mA cm^(-2)in a Zn-air battery system.This work presents a new strategy for the design and synthesis of efficient multifunctional carbon-based catalysts for energy storage and conversion devices.

Multiple-dimensioned defect engineering for graphite felt electrode of vanadium redox flow battery

The scarcity of wettability,insufficient active sites,and low surface area of graphite felt(GF)have long been suppressing the performance of vanadium redox flow batteries(VRFBs).Herein,an ultra-homogeneous multipledimensioned defect,including nano-scale etching and atomic-scale N,O codoping,was used to modify GF by the molten salt system.NH_(4)Cl and KClO_(3) were added simultaneously to the system to obtain porous N/O co-doped electrode(GF/ON),where KClO_(3) was used to ultra-homogeneously etch,and O-functionalize electrode,and NH4Cl was used as N dopant,respectively.GF/ON presents better electrochemical catalysis for VO_(2)+/VO_(2)+ and V3+/V2+ reactions than only O-functionalized electrodes(GF/O)and GF.The enhanced electrochemical properties are attributed to an increase in active sites,surface area,and wettability,as well as the synergistic effect of N and O,which is also supported by the density functional theory calculations.Further,the cell using GF/ON shows higher discharge capacity,energy efficiency,and stability for cycling performance than the pristine cell at 140 mA cm^(−2) for 200 cycles.Moreover,the energy efficiency of the modified cell is increased by 9.7% from 55.2% for the pristine cell at 260 mA cm^(−2).Such an ultra-homogeneous etching with N and O co-doping through“boiling”molten salt medium provides an effective and practical application potential way to prepare superior electrodes for VRFB.

基于n阶S形曲线的SCARA多目标运动规划

为了对SCARA机器人运动过程中产生的振动进行有效抑制,首先,建立了SCARA机器人的简化浮动坐标法动力学模型;然后,利用n阶S形曲线构造了同时对定位时间和SCARA机器人受到的冲击进行优化的多目标优化模型;最后,采用基于Kriging模型的NSGA-Ⅱ算法对优化问题进行求解。得到的多目标优化问题的Pareto前沿表明,四阶S形曲线的定位时间与三阶S形曲线大致相当,但是引起的冲击远小于三阶S形曲线。对优化结果的仿真也表明,以四阶S形曲线驱动的SCARA机器人运行过程更平滑,产生的残余振动也远小于三阶S形曲线。研究表明,四阶S形曲线具备比三阶S形曲线更加优良的振动抑制性能,在工程中具有广泛的应用价值。

Double-Doped Carbon-Based Electrodes with Nitrogen and Oxygen to Boost the Areal Capacity of Zinc-Bromine Flow Batteries

Ensuring a stable power output from renewable energy sources,such as wind and solar energy,depends on the development of large-scale and long-duration energy storage devices.Zinc–bromine fl ow batteries(ZBFBs)have emerged as cost-eff ective and high-energy-density solutions,replacing expensive all-vanadium fl ow batteries.However,uneven Zn deposition during charging results in the formation of problematic Zn dendrites,leading to mass transport polarization and self-discharge.Stable Zn plating and stripping are essential for the successful operation of high-areal-capacity ZBFBs.In this study,we successfully synthesized nitrogen and oxygen co-doped functional carbon felt(NOCF4)electrode through the oxidative polymerization of dopamine,followed by calcination under ambient conditions.The NOCF4 electrode eff ectively facilitates effi cient“shuttle deposition”of Zn during charging,signifi cantly enhancing the areal capacity of the electrode.Remarkably,ZBFBs utilizing NOCF4 as the anode material exhibited stable cycling performance for 40 cycles(approximately 240 h)at an areal capacity of 60 mA h/cm^(2).Even at a high areal capacity of 130 mA h/cm^(2),an impressive energy effi ciency of 76.98%was achieved.These fi ndings provide a promising pathway for the development of high-areal-capacity ZBFBs for advanced energy storage systems.

基于等效结构应力法的高强钢焊接结构低温主S-N曲线

现有的疲劳S-N曲线已不再适用于北极的低温环境,为了评估北极海洋工程设备材料的低温疲劳寿命,有必要建立金属结构尤其是焊接结构的低温疲劳S-N曲线。本文基于等效结构应力法,计算出Q690高强钢管环焊缝的主S-N曲线,并通过共振疲劳试验对该方法进行了验证。在此基础上,结合大量的高强钢焊接结构试验结果,将温度敏感因子c引入到低温疲劳主S-N曲线的推导中,首次建立了基于低温金属焊接结构的主S-N曲线,并对文献中的疲劳S-N试验数据和ASME中的修正方法进行了对比和验证。结果表明,等效结构应力法能够较准确地计算出焊缝疲劳S-N曲线,推导出的金属焊接结构低温主S-N曲线与试验曲线吻合较好,能够满足低温地区工程要求,可为高强钢焊接结构在北极地区低温环境中的广泛应用提供理论指导。该方法可以为金属焊接结构的低温疲劳研究节省大量的成本,减少非标准试验操作造成的不必要的误差。这对北极海洋工程设备的设计、安全运行和疲劳评估具有重要意义。

Rationally designed hollow carbon nanospheres decorated with S,P co-doped NiSe_(2) nanoparticles for high-performance potassium-ion and lithium-ion batteries

Hollow nanostructures with external shells and inner voids have been proved to greatly shorten the transport distance of ions/electrons and buffer volume change,especially for the large-sized potassium-ions in secondary batteries.In this work,hollow carbon(HC) nanospheres embedded with S,P co-doped NiSe_(2)nanoparticles are fabricated by "drop and dry" and "dissolving and precipitation" processes to form Ni(OH)2nanocrystals followed by annealing with S and P dopants to form nanoparticles.The resultant S,P-NiSe_(2)/HC composite exhibits excellent cyclic performance with 131.6 mA h g^(-1)at1000 mA g^(-1)after 3000 cycles for K^(+)storage and a capacity of 417.1 mA h g^(-1)at 1000 mA g^(-1)after1000 cycles for Li^(+)storage.K-ion full cells are assembled and deliver superior cycling stability with a ca pacity of 72.5 mA h g^(-1)at 200 mA g^(-1)after 500 cycles.The hollow carbon shell with excellent electrical conductivity effectively promotes the transporta tion and tolerates large volume variation for both K^(+)and Li^(+).Density functional theory calculations confirm that the S and P co-doping NiSe_(2) enables stronger adsorption of K^(+)ions and higher electrical conductivity that contributes to the improved electrochemical performance.

Construction of N,O co-doped carbon anchored with Co nanoparticles as efficient catalyst for furfural hydrodeoxygenation in ethanol

Hydrodeoxygenation of furfural(FF)into 2-methylfuran(MF)is a significant biomass utilization route.However,designing efficient and stable non-noble metal catalyst is still a huge challenge.Herein,we reported the N,O co-doped carbon anchored with Co nanoparticles(Co-SFB)synthesized by employing the organic ligands with the target heteroatoms.Raman,electron paramagnetic resonance(EPR),electrochemical impedance spectroscopy(EIS),and X-ray photoelectron spectroscopy(XPS)characterizations showed that the co-doping of N and O heteroatoms in the carbon support endows Co-SFB with enriched lone pair electrons,fast electron transfer ability,and strong metal-support interaction.These electronic properties resulted in strong FF adsorption as well as lower apparent reaction activation energy.At last,the obtained N,O co-doped Co/C catalyst showed excellent catalytic activity(nearly 100 mol%FF conversion and 94.6 mol%MF yield)and stability for in-situ dehydrogenation of FF into MF.This N,O co-doping strategy for the synthesis of highly efficient catalytic materials with controllable electronic state will provide an excellent opportunity to better understand the structure-function relationship.

GENERALIZED FORELLI-RUDIN TYPE OPERATORS BETWEEN SEVERAL FUNCTION SPACES ON THE UNIT BALL OF C^(N)

In this paper,we investigate sufficient and necessary conditions such that generalized Forelli-Rudin type operators T_(λ,τ,k),S_(λ,τ,k),Q_(λ,τ,k)and R_(λ,τ,k)are bounded between Lebesgue type spaces.In order to prove the main results,we first give some bidirectional estimates for several typical integrals.