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Phase-boundary regulation boosting electrochemical reactivity of tin-based anodes for magnesium-ion batteries

Science China Chemistry 2022年第7期65卷 1433-1444页

作者： Meijia Song Yan Wang Conghui Si Wenrun Cui wanfeng yang Guanhua Cheng Zhonghua Zhang Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials(Ministry of Education) School of Materials Science and EngineeringShandong UniversityJinan 250061China School of Materials Science and Engineering University of JinanJinan 250022China Shandong Provincial Key Laboratory of Processing and Testing Technology of Glass&Functional Ceramics School of Materials Science and EngineeringQilu University of Technology(Shandong Academy of Sciences)Jinan 250353China

Tin(Sn)-based materials are promising anodes for magnesium-ion batteries(MIBs) owing to their low reaction voltages, high theoretical specific capacities and good compatibility with conventional electrolytes. However, relatively arduous alloying reaction and sluggish diffusion kinetics limit their practical applications. Herein, we proposed a general strategy to regulate the electrochemical reactivity and performance of Sn-based anodes for Mg storage through the introduction of the second phase and phase boundary. The biphase Sn–Al, Sn–Pb and Sn–Zn O films were further fabricated via magnetron co-sputtering. Taking Sn–Al as an example, it has been revealed that the introduction of Al can effectively stimulate the electrochemical reaction of Sn with Mg in either nanoscale or bulk through combining experiments with density-functional theory calculations. Specially, the rolled Sn–Al electrode exhibits superior long-term stability over 5,000 cycles. Additionally, the Mg-storage mechanism of the Sn–Al electrode was investigated by operando X-ray diffraction. The Sn–Al anodes also demonstrate good compatibility with simple Mg-salt-based electrolytes like Mg(TFSI)2in full cells. More importantly, it has been authenticated that the activation effect of second phase and phase boundary to Sn is also applicable to Pb and Zn O. Our findings may provide a favorable reference for the development of alloy-type anodes for MIBs.

关键词： magnesium-ion batteries Sn-based anodes phase boundary magnetron sputtering density-functional theory calculation

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Self-templating synthesis and structural regulation of nanoporous rhodium-nickel alloy nanowires efficiently catalyzing hydrogen evolution reaction in both acidic and alkaline electrolytes

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Nano Research 2023年第2期16卷 2026-2034页

作者： Zhihua Zhai Yan Wang Conghui Si Pan Liu wanfeng yang Guanhua Cheng Zhonghua Zhang Key Laboratory for Liquid–Solid Structural Evolution and Processing of Materials(Ministry of Education) School of Materials Science and EngineeringShandong UniversityJinan 250061China School of Materials Science and Engineering University of JinanJinan 250022China Shandong Provincial Key Laboratory of Processing and Testing Technology of Glass&Functional Ceramics School of Materials Science and EngineeringQilu University of Technology(Shandong Academy of Sciences)Jinan 250353China Shanghai Key Laboratory of Advanced High Temperature Materials and Precision Forming School of Materials Science and EngineeringShanghai Jiao Tong UniversityShanghai 200240China

Highly active and stable electrocatalysts to produce hydrogen through water splitting are crucial for clean energy systems but are still challenging.Herein,a novel self-templating strategy was proposed to synthesize one-dimensional nanoporous RhNi alloy nanowires through combining metallurgical eutectic solidification and microalloying with chemical dealloying.In-situ X-ray diffraction and ex-situ characterizations reveal that the Al matrix served as a template to guide the growth of the Al3(Ni,Rh)nanowires during eutectic solidification of Al-Ni-Rh precursor and was completely removed in the dealloying process.Meanwhile,the nanowire morphology could be well retained and the dealloying of Al_(3)(Ni,Rh)led to the formation of nanoporous RhNi alloy nanowires.The length scale of the RhNi nanowires could be facilely regulated by changing the solidification conditions.More importantly,the RhNi catalysts show excellent electrocatalytic activity and stability towards hydrogen evolution reaction in both acidic and alkaline media,which has been rationalized by density functional theory calculations.

关键词： nanoporous alloys nanowires hydrogen evolution reaction density functional theory dealloying

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Dealloying-induced dual-scale nanoporous indium-antimony anode for sodium/potassium ion batteries

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Journal of Energy Chemistry 2022年第12期75卷 154-163,I0005页

作者： Hui Gao Yan Wang Zhiyuan Guo Bin Yu Guanhua Cheng wanfeng yang Zhonghua Zhang Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials(Ministry of Education) School of Materials Science and EngineeringShandong UniversityJinan 250061ShandongChina School of Materials Science and Engineering University of JinanJinan 250022ShandongChina

InSb alloy is a promising candidate for sodium/potassium ion batteries(SIBs/PIBs)but challenged with achieving high performance by dramatic volumetric changes.Herein,nanoporous(np)-InSb with dualscale phases(cubic/hexagonal(C/H)-InSb)was fabricated by chemical dealloying of ternary Mg-In-Sb precursor.Operando X-ray diffraction(XRD)and ex-situ characterizations well rationalize the dealloying/alloying mechanisms and the formation of dual-scale microstructures/phases.As an anode for SIB/PIBs,the np-InSb electrode exhibits superior reversible capacities and lifespan compared with the monometallic porous(p)-In electrode,stemming from the dealloying-induced dual-scale nanoporous architecture and alloying strategy with proper composition.The operando XRD results demonstrate that the(de)sodiated mechanism of the np-InSb electrode involves a two-step(de)alloying process,while the(de)potassiated mechanism is associated with a full electrochemically-driven amorphization upon cycling.Additionally,the gas evolution during the(dis)charge process was monitored by on-line mass spectrometry.

关键词： Sodium/potassium ion battery Indium-antimony anode Dealloying Operando X-ray diffraction On-line mass spectrometry

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Scalable fabrication of antimony nanoparticles confined in a porous carbon framework for high-performance sodium-ion batteries

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ChemPhysMater 2022年第2期1卷 112-118页

作者： Wensheng Ma wanfeng yang Weimin Wang Qingguo Bai Zhonghua Zhang Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials(Ministry of Education) School of Materials Science and EngineeringShandong UniversityJinan 250061China

Engineering of carbon/metal nanocomposites with small metal particles is promising for the development of alloy-type anodes.Herein,an Sb@C composite was developed from a commercial potassium antimony tartrate precursor using a scalable pyrolysis method.Ultrafine Sb nanoparticles are confined within a porous carbon framework,which substantially facilitates the diffusion of Na-ion/electrons and effectively alleviates the charg-ing/discharging induced volume change.The obtained Sb@C material displays excellent electrochemical perfor-mance for Na^(+) storage.The Na^(+) diffusion behavior of Sb@C was comprehensively investigated using various methods,and its gas evolution during the discharge/charge was monitored via online mass spectrometry.Then,Sb@C was assembled into full cells.During discharge/charge processes,the Na_(3)V_(2)(PO_(4))_(2)F_(3)/Sb@C full cells de-livered a competitive working voltage of 2.95 V and a capacity retention of 93.4%(50 cycles@0.2 A g^(−1)).Considering its facile preparation method from a commercial precursor,the Sb@C composite can potentially realize a large-scale application of sodium-ion batteries.

关键词： Pyrolysis method Antimony anodes Sodium-ion batteries Online DEMS

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Tungsten diselenide nanoplates as advanced lithium/ sodium ion electrode materials with different storage mechanisms

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Nano Research 2017年第8期10卷 2584-2598页

作者： wanfeng yang Jiawei Wang Conghui Si Zhangquan Peng Zhonghua Zhang Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials (Ministry of Education) School of Materials Science and Engineering Shandong University Jingshi Road 17923 Jinan 250061 China State Key Laboratory of Electroanalytical Chemistry Changchun Institute of Applied Chemistry Chinese Academy of Sciences Changchun 130022 China

Transition-metal dichalcogenides （TMDs） exhibit immense potential as lithium/ sodium-ion electrode materials owing to their sandwich-like layered structures. To optimize their lithium/sodium-storage performance, two issues should be addressed： fundamentally understanding the chemical reaction occurring in TMD electrodes and developing novel TMDs. In this study, WSe2 hexagonal nanoplates were synthesized as lithium/sodium-ion battery （LIB/SIB） electrode materials. For LIBs, the WSe2-nanoplate electrodes achieved a stable reversible capacity and a high rate capability, as well as an ultralong cycle life of up to 1,500 cycles at 1,000 mA·g^-1. Most importantly, in situ Raman spectroscopy, ex situ X-ray diffraction （XRD）, transmission electron microscopy, and electrochemical impedance spectroscopy measurements performed during the discharge-charge process clearly verified the reversible conversion mechanism, which can be summarized as follows： WSe2 ＋ 4Li^＋＋ 4e^- ←→ W ＋ 2Li2Se. The WSe2 nanoplates also exhibited excellent cycling performance and a high rate capability as SIB electrodes. Ex situ XRD and Raman spectroscopy results demonstrate that WSe2 reacted with Na^＋ more easily and thoroughly than with Li^＋ and converted to Na2Se and tungsten in the Ist sodiated state. The subsequent charging reaction can be expressed as Na2Se → Se ＋ 2Na^＋＋ 2e^-, which differs from the traditional conversion mechanism for LIBs. To our knowledge, this is the first systematic exploration of the lithium/sodium-storage performance of WSe2 and the mechanism involved.

关键词： lithium/sodium ion battery anodes WSe2 nanoplates X-ray diffraction Raman spectroscopy lithium/sodium storage mechanisms

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Dealloying-constructed hierarchical nanoporous bismuth-antimony anode for potassium ion batteries

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Fundamental Research 2021年第4期1卷 408-417页

作者： Hui Gao Kuibo Yin Zhiyuan Guo Ying Zhang Wensheng Ma wanfeng yang Ke Sun Zhangquan Peng Zhonghua Zhang Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials(Ministry of Education) School of Materials Science and EngineeringShandong UniversityJingshi Road 17923Jinan 250061China SEU-FEI Nano-Pico Center Key Lab of MEMS of Ministry of EducationSoutheast UniversityNanjing 210096China Laboratory of Advanced Spectro-electrochemistry and Li-ion Batteries Dalian Institute of Chemical PhysicsChinese Academy of SciencesDalian 116023China

Bi-Sb alloys are appealing anode materials for potassium ion batteries(PIBs)but challenged by their enormous volumetric variation during operation.Herein,a facile one-step dealloying protocol was devised and utilized to prepare the Bi-Sb alloys that manifest an exotic bicontinuous hierarchical nanoporous(np)microstructure ideal for volume-change mitigation and K+transport percolation.The growth mechanism fostering the peculiar morphology of the np-(Bi,Sb)alloys was investigated and clarified via operando X-ray(XRD)and ex-situ scanning electron microscopy(SEM).In particular,the np-Bi6Sb2 electrode,optimized for comprehensive electrochemical performance,achieves decent reversible capacities and a superior lifespan,as benchmarked with the monometallic references and other Bi-Sb alloy electrodes.The(de)potassiation mechanism of the np-(Bi,Sb)alloys was studied by operando XRD and further rationalized by density functional theory(DFT)calculations,whereby a homogeneous(segregation-free)and robust two-step electrochemically-driven phase transformations’catenation of(Bi,Sb)↔K(Bi,Sb)2↔K3(Bi,Sb)was reliably established to substantiate the outstanding reversibility of the np-(Bi,Sb)anodes in PIBs.

关键词： Potassium ion battery Bismuth-antimony anodes Density functional theory Dealloying Operando X-ray diffraction

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Tailoring MXene Thickness and Functionalization for Enhanced Room‑Temperature Trace NO_(2) Sensing

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Nano-Micro Letters 2024年第5期16卷 71-86页

作者： Muhammad Hilal Woochul yang Yongha Hwang wanfeng Xie Department of Physics Dongguk UniversitySeoul 04620Republic of Korea Department of Control and Instrumentation Engineering Korea UniversitySejong 30019Republic of Korea School of Electronics&Information University‑Industry Joint Center for Ocean Observation and Broadband CommunicationQingdao UniversityQingdao 266071China

In this study,precise control over the thickness and termination of Ti3C2TX MXene flakes is achieved to enhance their electrical properties,environmental stability,and gas-sensing performance.Utilizing a hybrid method involving high-pressure processing,stirring,and immiscible solutions,sub-100 nm MXene flake thickness is achieved within the MXene film on the Si-wafer.Functionalization control is achieved by defunctionalizing MXene at 650℃ under vacuum and H2 gas in a CVD furnace,followed by refunctionalization with iodine and bromine vaporization from a bubbler attached to the CVD.Notably,the introduction of iodine,which has a larger atomic size,lower electronegativity,reduce shielding effect,and lower hydrophilicity(contact angle:99°),profoundly affecting MXene.It improves the surface area(36.2 cm^(2) g^(-1)),oxidation stability in aqueous/ambient environments(21 days/80 days),and film conductivity(749 S m^(-1)).Additionally,it significantly enhances the gas-sensing performance,including the sensitivity(0.1119Ωppm^(-1)),response(0.2% and 23%to 50 ppb and 200 ppm NO_(2)),and response/recovery times(90/100 s).The reduced shielding effect of the–I-terminals and the metallic characteristics of MXene enhance the selectivity of I-MXene toward NO2.This approach paves the way for the development of stable and high-performance gas-sensing two-dimensional materials with promising prospects for future studies.

关键词： Controlled MXene thickness Gaseous functionalization approach Lower electronegativity functional groups Enhanced MXene stability Trace NO_(2)sensing

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紧邻地铁大型深基坑群坑施工方法研究

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建筑施工 2024年第2期46卷 218-221页

作者：宋自杰尤雪春杨万锋上海建工七建集团有限公司上海200050

以上海张江中区单元56-01地块、57-01地块项目基坑施工为背景工程,对群坑施工关键技术进行了研究。通过对群坑进行合理分区分块施工,地下室底板采用跳仓法施工,并在部分支撑上加设伺服轴力自动补偿系统,减少了基坑施工对邻近的轨道交通1... 详细信息

以上海张江中区单元56-01地块、57-01地块项目基坑施工为背景工程,对群坑施工关键技术进行了研究。通过对群坑进行合理分区分块施工,地下室底板采用跳仓法施工,并在部分支撑上加设伺服轴力自动补偿系统,减少了基坑施工对邻近的轨道交通13号线区间隧道的影响,为类似紧邻地铁的深基坑群坑施工提供了参考。

关键词：紧邻地铁大型深基坑群坑施工变形控制

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自动化抽取进口大豆检疫样品研究

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现代农业科技 2024年第1期 164-168页

作者：杨万风刘翔谌运清杨光张浩汪连军张扬赵光明邵沛泽连云港海关江苏连云港222042 连云港检验认证有限公司江苏连云港222042 南京海关江苏南京222001

随着我国进口大豆数量和规模的不断增加,大豆检疫取样工作中存在的问题突出。本文系统分析了大豆检疫样品的组成,总结了进口散装大豆检疫中取制样工作以人工操作为主的现状,设计研发了专门用于大豆检疫样品抽取的自动化取制样系统,可用... 详细信息

随着我国进口大豆数量和规模的不断增加,大豆检疫取样工作中存在的问题突出。本文系统分析了大豆检疫样品的组成,总结了进口散装大豆检疫中取制样工作以人工操作为主的现状,设计研发了专门用于大豆检疫样品抽取的自动化取制样系统,可用于代替人工开展进口大豆检疫样品的抽取,阐述了该设施的设计流程、取样过程和应用效果,并对系统工作效能进行了分析,对其推广应用开展了讨论,以期为进口大豆检疫取样分析的自动化提供参考。

关键词：进口大豆检疫样品自动化抽样

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Liquid metal assisted regulation of macro-/micro-structures and mechanical properties of nanoporous copper

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Science China(Technological Sciences) 2021年第10期64卷 2229-2236页

作者： ZHANG Ying BAI QingGuo yang wanfeng ZHANG ZhongHua Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials(Ministry of Education) School of Materials Science and EngineeringShandong UniversityJinan 250061China School of Applied Physics and Materials Wuyi UniversityJiangmen 529020China

Nanoporous metals have received significant attention as a new class of structural and functional materials.However,the macroscopic brittle fracture under the tensile test is an impediment to their practical applications.Thus,it is of central importance to develop nanoporous materials with low cost and high tensile ductility.Herein,a nanoporous Cu film supported on a pure Cu substrate(NPC@Cu)was fabricated by utilizing a liquid Ga assisted alloying-dealloying strategy,and the thickness of NPC film can be precisely regulated by changing the mass loading of liquid Ga.In-situ X-ray diffraction was performed to further explore the alloying/dealloying mechanisms.The NPC@Cu films show good tensile mechanical properties with a minimum elongation of 13.5%,which can be attributed to the good interface bonding and certain modulus matching between the nanoporous Cu layer and the Cu substrate.Our findings demonstrate that the design of film-substrate structure provides a feasible strategy for enhancing the mechanical properties of nanoporous metals.

关键词： nanoporous metals dealloying mechanical properties in-situ X-ray diffraction structural regulation

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