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dealloying induced nanoporosity evolution of less noble metals in Mg ion batteries

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Journal of Magnesium and Alloys 2021年第6期9卷 2122-2132页

作者： Jiazheng Niu Meijia Song Ying Zhang 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 250061P.R.China

Rechargeable Mg ion batteries(MIBs)have aroused great interests,and using alloy-type anodes and conventional electrolytes offers an effective way to develop high energy density Mg battery systems.However,the dealloying-induced nanoporosity evolution of alloy-type anodes during the charging process has received less attention.Herein,using a magnetron-sputtered Mg;Bi;film as an example,we investigate its electrochemical dealloying and associated structural evolution in an all-phenyl-complex electrolyte by in-situ and ex-situ characterizations.The microstructures and length scales of nanoporous Bi can be facilely regulated by changing electrochemical parameters,and there exists a good linear correlation between the surface diffusivity of Bi and the applied current density/potential scan rate on a logarithm scale.More importantly,the self-supporting nanoporous Bi electrodes deliver satisfactory Mg storage performance and alloy-type anodes show good compatibility with conventional electrolytes.Furthermore,the charging-induced dealloying in MIBs is a general strategy to fabricate nanoporous less noble metals like Sn,Pb,In,Cu,Zn and Al,which shows advantages over chemical dealloying in aqueous solutions.Our findings highlight the significance of nanoporosity evolution of alloy-type anodes during dealloying,and open opportunities for the fabrication of nanoporous reactive metals.

关键词： Mg ion batteries Alloy-type anodes dealloying Nanoporous metals Surface diffusivity

dealloying-derived nanoporous deficient titanium oxide as high-performance bifunctional sulfur host-catalysis material in lithium-sulfur battery

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Journal of Materials Science & Technology 2021年第25期84卷 124-132页

作者： Ning Liu Heng Ma Lu Wang Yan Zhao Zhumabay Bakenov Xin Wang School of Materials Science and Engineering Tianjin Key Laboratory of Materials Laminating Fabrication and Interface Control TechnologyHebei University of TechnologyTianjin 300130China Institute of Batteries LLC Department of Chemical and Materials EngineeringNational Laboratory AstanaNazarbayev University53 Kabanbay Batyr AvenueNur-Sultan 010000Kazakhstan South China Academy of Advanced Optoelectronics International Academy of Optoelectronics at ZhaoqingSouth China Normal UniversityGuangzhou 510006China

In this work,we report a facile dealloying strategy to tailor the surface state of nanoporous TiO_(2) towards high-efficiency sulfur host material for lithium-sulfur(Li-S)batteries.When used as a sulfur cathode material,the oxygen-deficient TiO_(2)-xexhibits enhanced lithium polysulfides(Li PS)adsorption and conversion kinetics that effectively tackle the shuttle effect in lithium-sulfur batteries.The excellent ability of the oxygen vacancy sites on TiO_(2)-xsurface to trap Li PS is proved by experimental observations and density functional theory(DFT)calculations.Meanwhile,it also promotes conversion kinetics of lithium polysulfides,as verified by the asymmetric cell experiment.Accordingly,compared with the S/TiO_(2) cathode,the oxygen-deficient S/TiO_(2)-xelectrode exhibits preeminent rate and cycling performance in lithium-sulfur batteries:it delivers an ultra-low capacity decay of 0.039%per cycle after 1000 cycles at 1 C.Tunning the surface state of metal oxides by dealloying method offers a new facile strategy to design efficient sulfur cathode materials for lithium-sulfur batteries.

关键词： Li-S battery Oxygen defects TiO_(2)-x dealloying Cathode

dealloying corrosion of anodic and nanometric Mg41Nd5 in solid solution-treated Mg-3Nd-1Li-0.2Zn alloy

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Journal of Materials Science & Technology 2021年第24期83卷 161-178页

作者： Gui-Jia Gao Mei-Qi Zeng En-Liang Zhang Rong-Chang Zeng Lan-Yue Cui Dao-kui Xu Feng-Qin Wang M.Bobby Kannan Corrosion Laboratory for Light Metals College of Materials Science and EngineeringShandong University of Science and TechnologyQingdao266590China School of Materials Science and Engineering Zhengzhou UniversityZhengzhou450002China Key Laboratory of Nuclear Materials and Safety Assessment Institute of Metal ResearchChinese Academy of SciencesShenyang110016China School of Engineering University of NewcastleCallaghanNew South Wales 2308Australia

The microstructure and chemical compositions of the solid solution-treated Mg-3 Nd-1 Li-0.2 Zn alloy were characterized using optical microscope,scanning electron microscope(SEM),transmission electron microscope(TEM),electron probe micro-analyzer(EPMA)and X-ray photoelectron spectroscopy(XPS).The corrosion behaviour of the alloy was investigated via electrochemical polarization,electrochemical impedance spectroscopy(EIS),hydrogen evolution test and scanning Kelvin probe(SKP).The results showed that the microstructure of the as-extruded Mg-3 Nd-1 Li-0.2 Zn alloy containedα-Mg matrix and nanometric second phase Mg_(41)Nd_(5).The grain size of the alloy increased significantly with the increase in the heat-treatment duration,whereas the volume fraction of the second phase decreased after the solid solution treatment.The surface film was composed of oxides(Nd_(2)O_(3),Mg O,Li_(2)O and Zn O)and carbonates(Mg CO3 and Li_(2)CO3),in addition to Nd.The as-extruded alloy exhibited the best corrosion resistance after an initial soaking of 10 min,whereas the alloy with 4 h-solution-treatment possessed the lowest corrosion rate after a longer immersion(1 h).This can be attributed to the formation of Nd-containing oxide film on the alloys and a dense corrosion product layer.The dealloying corrosion of the second phase was related to the anodic Mg_(41)Nd_(5)with a more negative Volta potential relative toα-Mg phase.The preferential corrosion of Mg_(41)Nd_(5)is proven by in-situ observation and SEM.The solid solution treatment of Mg-3 Nd-1 Li-0.2 Zn alloy led to a shift in corrosion type from pitting corrosion to uniform corrosion under long-term exposure.

关键词： Magnesium alloy Corrosion Second phase Rare metal dealloying

Rh/CeO_(2) composites prepared by combining dealloying with calcination as an efficient catalyst for CO oxidation and CH4 combustion

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Journal of Rare Earths 2022年第4期40卷 636-644,I0005页

作者： Dong Duan Chunxi Hao Gege He Yang Wen Zhanbo Sun School of Physics MOE Key Laboratory for Non-Equilibrium Synthesis and Modulation of Condensed MatterXi'an Jiaotong UniversityXi'an 710049China State Key Laboratory for Mechanical Behavior of Materials Xi'an Jiaotong UniversityXi'an 710049China Key Laboratory of Shaanxi for Advanced Functional Materials and Mesoscopic Physics Xi'an Jiaotong UniversityXi'an 710049China

In this paper,a series of Rh/CeO_(2) catalysts with three-dimensional porous nanorod frameworks and large specific surface area were prepared by chemical dealloying Al–Ce–Rh precursor alloys and then calcining in pure O_(2).The effects of the Rh content and calcination temperature on CO oxidation and CH_(4) combustion were studied,and the results reveal that the Rh/CeO_(2) catalysts produced by dealloying melt-spun Al_(91.3)Ce_(8)Rh_(0.7) alloy ribbons and then calcining at 500℃ exhibit the best catalytic activity,the reaction temperatures for the complete conversion of CO and CH_(4) are as low as 90 and 400℃,respectively.Furthermore,after 150 h of continuous testing at high concentrations of H2O and CO_(2),the nature of the catalyst is not irreversibly destroyed and can still return to its initial level of activity.This excellent catalytic activity is attributed to a portion of Rh being uniformly distributed on the CeO_(2) nanorod surface in the form of nanoparticles,forming strong Rh–CeO_(2) interfacial synergy.Another portion of Rh permeated into the CeO_(2) lattice,which results in a significant increase in the number of oxygen vacancies in CeO_(2),thus allowing more surface active oxygen to be adsorbed and converted from the gas phase.Moreover,the catalytic reaction can proceed even in an oxygen-free environment due to the excellent oxygen storage performance of the Rh/CeO_(2) catalyst.

关键词： Al-Ce-Rh ribbon dealloying Rh/CeO_(2)catalyst CO oxidation CH_(4)combustion Rare earths

Preparation of Flaky Hexagonal Nanoporous Au-Cu and Au Particles via dealloying

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Acta Metallurgica Sinica(English Letters) 2022年第11期35卷 1777-1786页

作者： Jing Deng Yuan-Yun Zhao Yong Shen Chuntao Chang Qiang Li School of Physics Science and Technology Xinjiang UniversityUrumqi 830046China Neutron Scattering Technical Engineering Research Center School of Mechanical EngineeringDongguan University of TechnologyDongguan 523808China Guangdong-HongKong-Macao Joint Laboratory for Neutron Scattering Science and TechnologyDongguan University of TechnologyDongguan 523808China Instituteof Metal Research Chinese Academy of SciencesShenyang 110016China

Nanoporous metals have attracted signifi cant attention owing to their excellent physical,chemical,and biological properties.However,preparing ultrafi ne nanoporous metal particles(1–5μm)with specifi c geometries remains challenging.Herein,we report a simple strategy to prepare ultrafi ne fl aky hexagonal nanoporous Au-Cu and Au particles via dealloying.Mg-based alloy ribbons with ultrafi ne fl aky hexagonal Mg-Au(Cu)-Gd particles dispersed in a Mg-Cu(Au)-Gd metallic glassy matrix were prepared.The size and morphology of the precipitated fl aky hexagonal Mg-Au(Cu)-Gd particles were controlled by the solidifi cation process of a Mg 61 Cu 21 Au 7 Gd 11 alloy melt.Ultrafi ne fl aky hexagonal nanoporous Au-Cu particles(diagonal diameter 2.58±0.44μm,ligament size~28 nm),Au-1 particles(diagonal diameter 2.38±0.35μm,ligament size~83 nm)and Au-2 particles(diagonal diameter 2.39±0.44μm,ligament size~66 nm)were prepared via ultrasonic-assisted dealloying of Mg 61 Cu 21 Au 7 Gd 11 alloy ribbons in 0.25 M HCl/ethanol,1 M HCl/ethanol and 0.25 M HNO 3/ethanol solutions,respectively.The ultrafi ne fl aky hexagonal nanoporous Au-Cu and Au particles with a large specifi c surface area have a uniform particle size and shape,implying that they possess adequate powder fl uidity and excellent catalytic properties.Moreover,the formation mechanism of the MgAu(Cu)Gd phase in solidifi ed Mg-Cu-Au-Gd alloys was discussed.This study provides a novel approach for synthesizing nanoporous metal particles with a specifi c geometry.

关键词： Metallic glasses Mg-based alloys dealloying Nanoporous particles Mg-Au-Gd phase

dealloying of an amorphous TiCuRu alloy results in a nanostructured electrocatalyst for hydrogen evolution reaction

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Carbon Energy 2023年第8期5卷 87-97页

作者： Jinsen Tian Yuanchao Hu Wenfei Lu Jiahua Zhu Xiaodi Liu Jun Shen Gang Wang Jan Schroers College of Mechatronics and Controlling Engineering Shenzhen UniversityShenzhenChina Shenzhen Key Laboratory of High Performance Nontraditional Manufacturing College of Mechatronics and Control EngineeringShenzhen UniversityShenzhenChina Department of Mechanical Engineering&Materials Science Yale UniversityNew HavenConnecticutUSA Department of Inorganic Materials School of Materials Science and EngineeringTongji UniversityShanghaiChina Laboratory for Microstructures Institute of MaterialsShanghai UniversityShanghaiChina

Development of an electrocatalyst that is cheap and has good properties to replace conventional noble metals is important for H_(2) applications.In this study,dealloying of an amorphous Ti_(37)Cu_(60)Ru_(3) alloy was performed to prepare a freestanding nanostructured hydrogen evolution reaction(HER)catalyst.The effect of dealloying and addition of Ru to TiCu alloys on the microstructure and HER properties under alkaline conditions was investigated.3 at.%Ru addition in Ti_(40)Cu_(60) decreases the overpotential to reach a current density of 10mA cm^(-2) and Tafel slope of the dealloyed samples to 35 and 34mV dec−1.The improvement of electrocatalytic properties was attributed to the formation of a nanostructure and the modification of the electronic structure of the catalyst.First-principles calculations based on density function theory indicate that Ru decreases the Gibbs free energy of water dissociation.This work presents a method to prepare an efficient electrocatalyst via dealloying of amorphous alloys.

关键词： amorphous alloy dealloying first-principles calculations HER TiCuRu

Facile synthesis of metal and alloy nanoparticles by ultrasound-assisted dealloying of metallic glasses

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Journal of Materials Science & Technology 2021年第23期82卷 144-152页

作者： Yuan-Yun Zhao Feng Qian Wenfeng Shen Chengliang Zhao Jianguo Wang Chunxiao Xie Fengling Zhou Chuntao Chang Yanjun Li Neutron Scattering Technical Engineering Research Center School of Mechanical EngineeringDongguan University of TechnologyDongguan523808China Department of Materials Science and Engineering Norwegian University of Science and TechnologyTrondheim7491Norway Ningbo Institute of Materials Technology and Engineering Chinese Academy of SciencesNingbo315201China School of Materials Science and Engineering Beijing Institute of TechnologyBeijing100081China Guangdong-Hong Kong-Macao Joint Laboratory for Neutron Scattering Science and Technology Dongguan University of TechnologyDongguan523808China

Metal and alloy nanoparticles synthesized by chemical reduction have attracted increasing attention due to their superior physical,chemical,and biological properties.However,most chemical synthesis processes rely on the use of harsh reducing agents and complicated chemical ingredients.Herein,we report a novel reduction-agent-free and surfactant(stabilizer)-free strategy to synthesize Cu,Ag,Au,Cu-Pt,Cu-Au,Cu-Au-Pt-Pd,and Au-Pt-Pd-Cu nanoparticles by ultrasound-assisted dealloying of Mgbased metallic glasses.The formation mechanism of the metal and alloy nanoparticles is revealed by a detailed investigation of sequential intermediate products.We demonstrate that the glass-liquid phase transition of the initially dealloying metallic glasses,together with the synergistic effect of dealloying and ultrasound-driven ligament-breakage of small enough nanoporous intermediates,play key roles in preparing the uniformly dispersed metal and alloy nanoparticles.This approach greatly simplifies the up-scaling synthesis of monometallic and bimetallic nanoparticles,and also provides a general strategy for synthesizing unprecedented multimetallic nanoparticles.

关键词： Metallic glasses dealloying Ultrasound Nanoparticles Multimetallic nanoparticles

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

Fabrication of nanoporous Ni and NiO via a dealloying strategy for water oxidation catalysis

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Journal of Energy Chemistry 2020年第11期29卷 125-134页

作者： Xiangrong Ren Yiyue Zhai Qi Zhou Junqing Yan Shengzhong Liu Key Laboratory of Applied Surface and Colloid Chemistry Ministry of EducationShaanxi Engineering Lab for Advanced Energy TechnologySchool of Materials Science and EngineeringShaanxi Normal UniversityXi'an 710119ShaanxiChina State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals Lanzhou University of TechnologyLanzhou 730050GansuChina Materials Science and Engineering College Lanzhou University of TechnologyLanzhou 730050GansuChina

Nickel oxides and(oxy)hydroxides are promising replacements for noble-metal-based catalysts owing to their high activity and good long-term stability for the oxygen evolution reaction(OER). Herein, we developed nanoporous Ni by a method of combined rapid solidification and chemical dealloying. Subsequently,nanoporous Ni O was obtained via heating treatment, the macropore and skeleton sizes of the NiO originated from Ni10Al90 alloy are 100–300 nm and 80–200 nm, respectively. Benefiting from the multi-stage nanoporous structure and high specific surface area, the nanoporous NiO demonstrates an outstanding OER, reaching 20 mA cm-2 at an overpotential of 356 mV in 1 M KOH. The corresponding Tafel slope and apparent activation energy are measured to be 76.73 mV dec-1 and 29.0 kJ mol-1, respectively. Moreover,kinetic analysis indicates that the Ni O catalyst shows pseudocapacitive characteristics, and the improved current is attributed to the high-rate pseudocapacitive behavior that efficiently maintains increased nickel redox cycling to accelerate the reaction rates. After 1000 cycles of voltammetry, the overpotential of the NiO decreases by 22 mV(j = 10 mA cm-2), exhibiting excellent stability and durability.

关键词： Rapid solidification dealloying Nanoporous Ni Electrocatalyst OER