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

Journal of Energy Chemistry 2024年第1期88卷 421-427,I0010页

作者： Quanqing Zhao Ruru Wang Ming Gao Bolin Liu Jianfeng Jia Haishun Wu Youqi Zhu Chuanbao Cao Key Laboratory of Magnetic Molecules and Magnetic Information Materials of Ministry of Education School of Chemistry and Materials ScienceShanxi Normal UniversityTaiyuan 030032ShanxiChina Metals and Chemistry Research Institute China Academy of Railway Sciences Corporation LimitedBeijing 100081China Research Center of Materials Science Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green ApplicationsBeijing Institute of TechnologyBeijing 100081China

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.

关键词： Sodium ion battery Oxide cathode phase engineering phase diagram Na~+kinetic

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phase engineering of Ni-Mn binary layered oxide cathodes for sodiumion batteries

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Journal of Energy Chemistry 2024年第4期91卷 501-511页

作者： Feifei Hong Xin Zhou Xiaohong Liu Guilin Feng Heng Zhang Weifeng Fan Bin Zhang Meihua Zuo Wangyan Xing Ping Zhang Hua Yan Wei Xiang College of Materials and Chemistry&Chemical engineering Chengdu University of TechnologyChengdu 610059SichuanChina College of Chemical engineering Sichuan UniversityChengdu 610065SichuanChina Research Institute for Electronic Science(RIES)and Division of Information Science and Technology Graduate School of Information Science and TechnologyHokkaido UniversityN20W10SapporoHokkaido 001-0020Japan School of Materials Science and engineering Suzhou University of Science and TechnologySuzhou 215009JiangsuChina Yibin Libode New Materials Co. Ltd.Yibin 644200SichuanChina engineering Research Center of the Ministry of Education for Advanced Battery Materials School of Metallurgy and EnvironmentCentral South UniversityChangsha 410083HunanChina

Nickel-manganese binary layered oxides with high working potential and low cost are potential candidates for sodium-ion batteries,but their electrochemical properties are highly related to compositional diversity.Diverse composite materials with various phase structures of P3,P2/P3,P2,P2/O3,and P2/P3/O3 were synthesized by manipulating the sodium content and calcination conditions,leading to the construction of a synthetic phase diagram for Na_(x)Ni_(0.25)Mn_(0.75)O_(2)(0.45≤x≤1.1).Then,we compared the electrochemical characteristics and structural evolution during the desodiation/sodiation process of P2,P2/P3,P2/03,and P2/P3/O3-Na_(x)Ni_(0.25)Mn_(0.75)O_(2).Among them,P2/P3-Na0.75Ni0.25Mn0.75O2exhibits the best rate capability of 90.9 mA h g^(-1)at 5 C,with an initial discharge capacity of 142.62 mA h g^(-1)at 0.1 C and a capacity retention rate of 78.25%after 100 cycles at 1 C in the voltage range of 2-4.3 V.The observed superior sodium storage performance of P2/P3 hybrids compared to other composite phases can be attributed to the enhanced Na^(+)transfer dynamic,reduction of the Jahn-teller effect,and improved reaction reversibility induced by the synergistic effect of P2 and P3 phases.The systematic research and exploration of phases in Na_(x)Ni_(0.25)Mn_(0.75)O_(2)provide new sights into high-performance nickel-manganese binary layered oxide for sodium-ion batteries.

关键词： phase engineering Ni-Mn layered oxide Cathode Sodium-ion batteries

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Size-Dependent Oxidation-Induced phase engineering for MOFs Derivatives Via Spatial Confinement Strategy Toward Enhanced Microwave Absorption

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Nano-Micro Letters 2022年第6期14卷 294-307页

作者： Hanxiao Xu Guozheng Zhang Yi Wang Mingqiang Ning Bo Ouyang Yang Zhao Ying Huang Panbo Liu School of Chemistry and Chemical engineering μNorthwestern Polytechnical UniversityXi’an 710129People’s Republic of China Key Laboratory of Magnetic Materials and Devices Ningbo Institute of Materials Technology&EngineeringChinese Academy of SciencesNingbo 315201People’s Republic of China MIIT Key Laboratory of Semiconductor Microstructure and Quantum Sensing Nanjing University of Science and TechnologyNanjing 210094People’s Republic of China Department of Mechanical and Materials engineering University of Western OntarioLondonON N6A 5B9Canada

Precisely reducing the size of metal-organic frameworks(MOFs)derivatives is an effective strategy to manipulate their phase engineering owing to size-dependent oxidation;however,the underlying relationship between the size of derivatives and phase engineering has not been clarified so far.Herein,a spatial confined growth strategy is proposed to encapsulate small-size MOFs derivatives into hollow carbon nanocages.It realizes that the hollow cavity shows a significant spatial confinement effect on the size of confined MOFs crystals and subsequently affects the dielectric polarization due to the phase hybridization with tunable coherent interfaces and heterojunctions owing to size-dependent oxidation motion,yielding to satisfied microwave attenuation with an optimal reflection loss of-50.6 d B and effective bandwidth of 6.6 GHz.Meanwhile,the effect of phase hybridization on dielectric polarization is deeply visualized,and the simulated calculation and electron holograms demonstrate that dielectric polarization is shown to be dominant dissipation mechanism in determining microwave absorption.This spatial confined growth strategy provides a versatile methodology for manipulating the size of MOFs derivatives and the understanding of size-dependent oxidation-induced phase hybridization offers a precise inspiration in optimizing dielectric polarization and microwave attenuation in theory.

关键词： Size-dependent oxidation phase engineering Coherent interface Dielectric polarization Electron holography

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phase engineering of metal nanocatalysts for electrochemical CO_(2) reduction

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eScience 2022年第5期2卷 467-485页

作者： Yanjie Zhai Peng Han Qinbai Yun Yiyao Ge Xiao Zhang Ye Chen Hua Zhang Department of Mechanical engineering The Hong Kong Polytechnic UniversityHung HomKowloonHong KongChina Department of Chemistry The Chinese University of Hong KongHong KongChina Department of Chemistry City University of Hong KongHong KongChina Hong Kong Branch of National Precious Metals Material engineering Research Center(NPMM) City University of Hong KongHong KongChina Shenzhen Research Institute City University of Hong KongShenzhen 518057China

The electrochemical CO_(2) reduction reaction(CO_(2)RR)offers a green and sustainable process to convert CO_(2) into valuable chemical stocks and fuels.Metal is one of the most promising types of catalysts to drive an efficient and selective CO_(2)RR.The catalytic performance of metal nanocatalysts is strongly dependent on their structural features.Recently,phase engineering of nanomaterials(PEN)has emerged as a prominent tactic to regulate the catalytic performance of metal nanocatalysts for the CO_(2)RR.A broad range of metal nanocatalysts with conventional and unconventional crystal phases has been developed,and remarkable achievements have been made.This review summarizes the most recent developments in phase engineering of metal nanocatalysts for the electrochemical CO_(2)RR.We first introduce the different crystal phases of metal nanocatalysts used in the CO_(2)RR and then discuss various synthetic strategies for unconventional phases of metal nanocatalysts.After that,detailed discussions of metal nanocatalysts with conventional and unconventional phases,including amorphous phases,are presented.Finally,the challenges and perspectives in this emerging area are discussed.

关键词： phase engineering CO_(2)reduction Metal nanocatalysts Electrocatalysis

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Li intercalation in an MoSe_(2) electrocatalyst:In situ observation and modulation of its precisely controllable phase engineering for a high-performance flexible Li-S battery

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Carbon Energy 2023年第2期5卷 201-215页

作者： Yunke Wang Yige Zhao Kangli Liu Shaobin Wang Neng Li Guosheng Shao Feng Wang Peng Zhang State Center for International Cooperation on Designer Low-carbon&Environmental Materials(CDLCEM) Zhengzhou UniversityZhengzhouChina Zhengzhou Materials Genome Institute(ZMGI) XingyangZhengzhouChina School of Chemical engineering and Advanced Materials The University of AdelaideAdelaideSouth AustraliaAustralia State Key Laboratory of Silicate Materials for Architecture Wuhan University of TechnologyWuhanChina Beijing Key Laboratory of Electrochemical Process and Technology for Materials Beijing University of Chemical TechnologyBeijingChina

Sophisticated efficient electrocatalysts are essential to rectifying the shuttle effect and realizing the high performance of flexible lithium-sulfur batteries(LSBs).phase transformation of MoSe_(2) from the 2H phase to the 1T phase has been proven to be a significant method to improve the catalytic activity.However,precisely controllable phase engineering of MoSe_(2) has rarely been reported.Herein,by in situ Li ions intercalation in MoSe_(2),a precisely controllable phase evolution from 2H-MoSe_(2) to 1T-MoSe_(2) was realized.More importantly,the definite functional relationship between cut-off voltage and phase structure was first identified for phase engineering through in situ observation and modulation methods.The sulfur host(CNFs/1T-MoSe_(2))presents high charge density,strong polysulfides adsorption,and catalytic kinetics.Moreover,Li-S cells based on it display capacity retention of 875.3mAh g^(-1) after 500 cycles at 1 C and an areal capacity of 8.71mAh cm^(-2) even at a high sulfur loading of 8.47mg cm^(-2).Furthermore,the flexible pouch cell exhibiting decent performance will endow a promising potential in the wearable energy storage field.This study proposes an effective strategy to precisely control the phase structure of MoSe_(2),which may provide the reference to fabricate the highly efficient electrocatalysts for LSBs and other energy systems.

关键词： electrocatalysts electrospinning Li intercalation lithium-sulfur batteries phase engineering

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Controlled vapour growth and phase engineering of large-area bilayer WSe2 for optoelectronic applications

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Progress in Natural Science:Materials International 2023年第6期33卷 947-953页

作者： Zhikang Ao Xiangdong Yang Xiang Lan Fen Zhang Yang Du Le Gao Xuyang Zhang Baihui Zhang Shunhui Zhang Tian Zhang Yinghao Chen Jianing Xie Wenkui Wen Chenyang Zha Huifang Ma Zhengwei Zhang College of Physics and Electronics Central South University School of Flexible Electronics(Future Technologies) & Institute of Advanced Materials(IAM) Jiangsu National Synergetic Innovation Center for Advanced MaterialsNanjing Tech University Institute of Micro/Nano Materials and Devices Ningbo University of Technology College of Materials Science and engineering Hunan University College of Energy and Power engineering Changsha University of Science and Technology Institute of Applied Physics and Materials engineering(IAPME) Zhuhai UM Science & Technology Research Institute(ZUMRI) University of Macau

The engineering of stacking order plays an important role in regulations of electronic and optical properties of layered van der Waals materials.Here,we demonstrate a developed physical vapour deposition approach to grow WSe2 atomic layers with controllable 3R and 2H phases.The 3R WSe2bilayer tends to form at a lower deposition temperature(830℃),and the 2H WSe2bilayer prefers to grow at a higher deposition temperature(930℃).Efficient phase engineering was demonstrated by simply controlling the deposition temperature.Moreover,by photoluminescence,Raman,selected area electron diffraction and so on,it was determined that the AA’-stacking corresponds to the 2H phase,and the AB-stacking corresponds to the 3R phase.So,different layer stacking and interlayer coupling result in differences in the optical and optoelectronic properties of the two phases.The responsivity of 3R bilayer WSe2is ～195 times higher than 2H phase exhibiting dramatically improved photoelectric detection performance by phase engineering(R3R=2.54 A/W vs R2H=0.013 A/W at 780 nm,82.7 mW cm-2).Hence,the findings of this study not only contribute to the controllable synthesis of two-dimensional materials with diverse stacking phases but also hold promise for advancing the design and fabrication of future optoelectronic devices.

关键词： 3R stacking Optoelectronics phase engineering Transition metal dichalcogenides WSe2

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Support induced phase engineering toward superior electrocatalyst

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Nano Research 2022年第3期15卷 1831-1837页

作者： Beibei Sheng Dengfeng Cao Hongwei Shou Oyawale Adetunji Moses Wenjie Xu Yujian Xia Yuzhu Zhou Huijuan Wang Ping Wan Shuang Zhu Wangsheng Chu Xiaojun Wu Shuangming Chen Li Song National Synchrotron Radiation Laboratory CAS Center for Excellence in NanoscienceUniversity of Science and Technology of ChinaHefei 230026China Hefei National Laboratory for Physical Sciences at the Microscales Department of Materials Sciences and EngineeringUniversity of Science and Technology of ChinaHefei 230026China Experimental Center of engineering and Material Science University of Science and Technology of ChinaHefei 230026China Materials Interfaces Center Shenzhen Institutes of Advanced TechnologyChinese Academy of SciencesShenzhen 440305China Institute of Energy Hefei Comprehensive Nation Science CenterHefei 230031China

The phase transformation of catalysts has been extensively observed in heterogeneous catalytic reactions that hinder the long cycling catalysis,and it remains a big challenge to precisely control the active phase during the complex conditions in electrochemical catalysis.Here,we theoretically predict that carbon-based support could achieve the phase engineering regulation of catalysts by suppressing specific phase transformation.Taken single-walled carbon nanotube(SWCNT)as typical support,combined with calculated E-pH(Pourbaix)diagram and advanced synchrotron-based characterizations technologies prove there are two different active phases source from cobalt selenide which demonstrate that the feasibility of using support effect regulating the potential advantageous catalysts.Moreover,it is worth noting that the phase engineering derived Co_(3)O_(4)-SWCNT exhibits a low overpotential of 201 mV for delivering the current density of 10 mA/cm^(2)in electrocatalytic oxygen evolution reaction(OER).Also,it reaches a record current density of 529 mA/cm^(2)at 1.63 V(vs.RHE)in the electrocatalytic urea oxidation reaction(UOR),overwhelming most previously reported catalysts.

关键词： phase engineering support synchrotron radiation characterization oxygen evolution reaction(OER) urea oxidation reaction(UOR)

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phase engineering oriented defect-rich amorphous/crystalline RuO_(2) nanoporous particles for boosting oxygen evolution reaction in acid media

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Nano Research Energy 2023年第3期2卷 48-55页

作者： Chengming Wang Qinghong Geng Longlong Fan Jun-Xuan Li Lian Ma Cuiling Li Key Laboratory of Cluster Science Ministry of EducationBeijing Key Laboratory of Photoelectronic/Electrophotonic Conversion MaterialsSchool of Chemistry and Chemical EngineeringBeijing Institute of TechnologyBeijing 100081China CAS Key Laboratory of Bio-inspired Materials and Interfacial Science Technical Institute of Physics and ChemistryChinese Academy of SciencesBeijing 100190China Binzhou Institute of Technology Binzhou 256600China

Imposing phase engineering to porous materials is promising to realize outperforming electrocatalytic performances by taking advantages of the merits of porous nanoarchitecture and heterophase structure.In this work,amorphous/crystalline ruthenium oxide(RuO_(2))porous particles with rationally regulated heterophases are successfully prepared by integrating the phase engineering into the porous material synthesis.The resultant defect-rich amorphous/crystalline RuO_(2)porous particles exhibit excellent electrocatalytic performance toward the oxygen evolution reaction,achieving a low overpotential of 165 mV at a current density of 10 mA·cm^(−2)and a high mass activity up to 133.8 mA·cm^(-2)at a low overpotential of 200 mV.This work indicates that the synergistic effect of amorphous/crystalline heterophase and porous structural characteristics enables RuO_(2)to trigger a superior electrocatalytic activity.

关键词： porous material phase engineering ruthenium oxide(RuO_(2)) oxygen evolution reaction(OER) electrocatalysis

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phase engineering of metal-organic frameworks

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Aggregate 2022年第1期3卷 93-107页

作者： Chen Ma Long Zheng Gang Wang Jun Guo Liuxiao Li Qiyuan He Ye Chen Hua Zhang Department of Chemistry The Chinese University of Hong KongShatinHong KongChina Department of Chemistry City University of Hong KongKowloonHong KongChina Department of Materials Science and engineering City University of Hong KongKowloonHong KongChina Hong Kong Branch of National Precious Metals Material Engineering Research Center(NPMM)City University of Hong KongKowloonHong KongChina Shenzhen Research Institute City University of Hong KongShenzhenChina

As an important category of porous crystalline materials,metal-organic frameworks(MOFs)have attracted extensive research interests owing to their unique structural features such as tunable pore structure and enormous surface area.Besides controlling the size,dimensionality,and composition of MOFs,further exploring the crystal-phase-dependent physicochemical properties is essential to improve their performances in various applications.Recently,great progress has been achieved in the phase engineering of nanomaterials(PEN),which provides an effective strategy to tune the functional properties of nanomaterials by modulating the arrangement of atoms.In this review,we adopt“phase”instead of“topology”to describe the crystal structure of MOFs and summarize the recent advances in phase engineering of MOFs.The two main strategies used to control the phase of MOFs,that is,phasecontrolled synthesis and phase transformation of MOFs,will be highlighted.The roles of various reaction parameters in controlling the crystal phase of MOFs are discussed.Then,the phase dependence of MOFs in various applications including luminescence,adsorption,and catalysis are introduced.Finally,some personal perspectives about the challenges and opportunities in this emerging field are presented.

关键词： crystal phase metal-organic frameworks phase engineering phase transformation phase-controlled synthesis

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engineering the high-entropy phase of Pt-Au-Cu nanowire for electrocatalytic hydrogen evolution

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Nano Research 2023年第8期16卷 10742-10747页

作者： Yanan Yu Guangdong Liu Shuaihu Jiang Ruya Zhang Huiqiu Deng Eric AStach Shujuan Bao Zhenhua Zeng Yijin Kang Institute of Fundamental and Frontier Sciences University of Electronic Science and Technology of ChinaChengdu 610054China School of Physics and Electronics Hunan UniversityChangsha 410082China Department of Materials Science and engineering University of PennsylvaniaPhiladelphiaPA 19104USA Institute for Clean Energy&Advanced Materials School of Materials and EnergySouthwest UniversityChongqing 400715China Davidson School of Chemical engineering Purdue UniversityWest LafayetteIN 47907USA

Hydrogen economy,as the most promising alternative energy system,relies on the hydrogen production through sustainable water splitting which in turn relies on the high efficiency electrocatalysts.PtAuCu A1-phase alloy has been predicted to be a promising electrocatalyst for the hydrogen evolution.As such preferred phase of Pt-Au-Cu is not thermodynamically favored,herein,we stabilize PtAuCu alloy by engineering the high-entropy phase in the form of nanowire.Density functional theory(DFT)calculations indicate that,in comparison with the ordered phase and segregated phases with discrete hydrogen binding energy,the high-entropy phase provides a diverse combination of site composition to continuously tune the hydrogen binding energy,and thus generate a series of highly active sites for the hydrogen evolution.Reflecting the theoretical prediction,electrochemical tests show that the A1-phase PtAuCu nanowire significantly outperforms its nanoparticle counterpart with phase segregation,toward the electrocatalysis of hydrogen evolution,offering one of the best hydrogen evolution electrocatalysts.

关键词： hydrogen evolution reaction phase engineering high entropy alloys

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