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A comprehensive understanding of the anionic redox chemistry in layered oxide cathodes for sodium-ion batteries

Science China Chemistry 2021年第3期64卷 385-402页

作者： Junteng Jin Yongchang Liu Xuelu Pang Yao Wang xianran xing Jun Chen Beijing Advanced Innovation Center for Materials Genome Engineering Department of Physical ChemistryUniversity of Science and Technology BeijingBeijing 100083China Beijing Advanced Innovation Center for Materials Genome Engineering Institute for Advanced Materials and TechnologyUniversity of Science and Technology BeijingBeijing 100083China

Sodium-ion batteries(SIBs) have demonstrated great application prospects in large-scale energy storage systems and low-speed electric vehicles due to the cost effectiveness and abundant resources. Layered transition-metal oxides are recognized as one of the most attractive sodium-ion storage cathode candidates by virtue of their high compositional diversity, environmental friendliness, ease of synthesis, and promising theoretical capacities. The practicability, however, is still limited by the fact that the energy densities of most Na-storage layered oxide cathodes solely using the conventional cationic redox are not comparable to those of the lithium-ion storage counterparts. Recently, the strategy of activating anionic redox(O^(2-)/O^(n-)) which is popular in Li-rich layered materials has been successfully applied in oxide cathodes of SIBs to promote the energy density to a new level. It is interesting to note that excess Na is not the prerequisite to induce anionic redox in sodium oxides, indicating a new mechanism underlying Na-ion materials. Herein, the latest advances on the anionic redox chemistry in layered oxide cathodes for SIBs,including the fundamental theories, triggering strategies, and applicable cathode materials, are comprehensively ***, the challenges(mainly O_(2) release) facing anionic redox are discussed, and the possible remedies are outlined for future developments toward a highly reversible oxygen usage. We believe that this review can provide a valuable guidance for the exploration of high-energy layered oxide cathode materials of SIBs.

关键词： sodium-ion batteries layered oxide cathodes anionic redox high energy density charge compensation mechanism

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Semi-empirical estimation for enhancing negative thermal expansion in PbTiO_(3)-based perovskites

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International Journal of Minerals,Metallurgy and Materials 2022年第4期29卷 783-786页

作者： Tao Yang Longlong Fan Yilin Wang Kun Lin Jun Chen xianran xing Beijing Advanced Innovation Center for Materials Genome Engineering Institute of Solid State ChemistryDepartment of Physical ChemistryUniversity of Science and Technology BeijingBeijing 100083China College of Physics and Materials Science Tianjin Normal UniversityTianjin 300387China Institute of Advanced Materials Jiangsu National Synergetic Innovation Center for Advanced MaterialsNanjing Tech UniversityNanjing 211816China

Generally,most materials expand when heated and contract when cooled,whereas negative thermal expansion(NTE)materials are very *** a typical NTE material,PbTiO_(3) and related compounds have drawn particular interest in recent *** discovery of an enhanced NTE system in PbTiO_(3) is beneficial to deepen our understanding of its mechanism and regulate its *** present,the method of discriminating an enhanced NTE material based on PbTiO_(3) is not ***,we propose a semi-empirical method through evaluating the average lattice distortion in related systems to estimate the relative coefficient of thermal expansion *** rationality of the method was verified by the analysis of the 0.6PbTiO_(3)-0.4Bi(Ga_(x)Fe_(1-x))O_(3) *** far,all PbTiO_(3)-based compounds with enhanced NTE conform well to this *** method provides the possibility to find more enhanced NTE PbTiO_(3)-based materials.

关键词： enhanced negative thermal expansion crystal structure lead titanate spontaneous polarization

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Calibration of local chemical pressure by optical probe

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National Science Review 2023年第9期10卷 258-269页

作者： Xiao Zhou Mei-Huan Zhao Shan-Ming Yao Hongliang Dong Yonggang Wang Bin Chen xianran xing Man-Rong Li Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education School of ChemistrySun Yat-sen University Center for High Pressure Science and Technology Advanced Research School of Materials Science and Engineering Peking University Beijing Advanced Innovation Center for Materials Genome Engineering Institute of Solid State Chemistry University of Science and Technology Beijing School of Science Hainan University

Chemical stabilization of a high-pressure metastable state is a major challenge for the development of advanced *** chemical pressure(Pchem) can effectively simulate the effect of physical pressure(Pphy)) experimental calibration of the pressure passed to local structural motifs,denoted as local chemical pressure(Pchem-△) which significantly governs the function of solid materials,remains absent due to the challenge of probing *** we establish an innovative methodology to experimentally calibrate the Pchem-△and build a bridge between Pchemand Pphyvia an optical probe ***-selective Bi3+-traced REVO4(RE=Y,Gd) is adopted as a prototype to introduce Bi3+optical probes and on-site sense of the Pchem-△experienced by the *** cell compression of RE0.9gBi0.02VO4under Pphyis chemically simulated by smaller-ion substitution(Sc3+→RE3+) in *** consistent red shift(△λ) of the emission spectra of Bi3+,which is dominated by locally pressure-induced REO8dodecahedral variation in RE0.98Bi0.02VO4(Pphy) and RE0.98-xScxBi0.02VO4(Pchem-△),respectively,is evidence of their similar pressure-dependent local structure *** innovative △λ-based experimental calibration of Pchem-△in the crystal-field dimension portrays the anisotropic transmission of Pchemto the local structure and builds a bridge between Pchem-△and Pphyto guide a new perspective for affordable and practical interception of metastable states.

关键词： chemical pressure high pressure ion substitution optical parameter spectra shift pressure calibration

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Novel thermal expansion of lead titanate

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Rare Metals 2003年第4期22卷 294-297页

作者： xing xianran, DENG Jinxia, CHEN Jun and LIU GuirongDepartment of Physical Chemistry, University of Science & Technology Beijing, Beijing 100083, China Department of Physical Chemistry University of Science & Technology Beijing 北京 100083

Lattice parameters of lead titanate were precisely re-determined in thetemperature range of-150-950 deg C by high precision XRPD measurements. It was clarified that therewas no any evidence for a new phase transition at low tempera-lures. Tetragonal distortion straindecreases with temperature increasing. A novel thermal expansion was observed, positive thermalexpansion from -150 deg C to room temperature (RT) and above 490 deg C, and the negative thermalexpansion in the temperature range of RT-490 deg C. A big jump of thermal expansion coefficient isattributed to the tetragonal-cubic phase transition. A rationalization for the negative thermalexpansion of PbTiO_3 is due to the decrease of anion-anion repulsion as polyhedra become moreregular at heating. The mechanisms of positive and negative thermal expansions were elucidated asthe same nature in the homogenous tetragonal phase at present case.

关键词： metallurgical physical chemistry thermal expansion X-ray powder diffraction(XRPD) lead titanate phase transition

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Chemical order-disorder nanodomains in Fe3Pt bulk alloy

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National Science Review 2022年第12期9卷 211-219页

作者： Qiang Li Yang Ren Qinghua Zhang Lin Gu Qingzhen Huang Hui Wu Jing Sun Yili Cao Kun Lin xianran xing Beijing Advanced Innovation Center for Materials Genome Engineering Institute of Solid State Chemistry University of Science and Technology Beijing X-Ray Science Division Argonne National Laboratory Beijing National Laboratory for Condensed Matter Physics Institute of Physics Chinese Academy of Sciences NIST Center for Neutron Research National Institute of Standards and Technology

Chemical ordering is a common phenomenon and highly correlated with the properties of solid *** means of the redistribution of atoms and chemical bonds,it invokes an effective lattice adjustment and tailors corresponding physical *** date,however,directly probing the 3D interfacial interactions of chemical ordering remains a big *** this work,we deciphered the interlaced distribution of nanosized domains with chemical order/disorder in Fe3pt bulk *** F-STEM images evidence the existence of such *** reverse Monte Carlo method with the X-ray pair distribution function data reveal the 3D distribution of local structures and the tensile effect in the disordered domains at the single-atomic *** chemical bonding around the domain boundary changes the bonding feature in the disordered side and reduces the local magnetic moment of Fe *** results in a suppressed negative thermal expansion and extended temperature range in Fe3Pt bulk alloy with *** study demonstrates a local revelation for the chemical order/disorder nanodomains in bulk *** understanding gained from atomic short-range interactions within the domain boundaries provides useful insights with regard to designing new functional compounds.

关键词： Fe3Pt alloy chemical order nanodomain local structure pair distribution function

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A new method to enhance the magnetocaloric effect in (Sc,Ti)Fe_(2) via magnetic phase separation

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Journal of Materials Science & Technology 2023年第16期147卷 102-111页

作者： Yuzhu Song Meng Xu Xinqi Zheng Chang Zhou Naike Shi Qingzhen Huang Shouguo Wang Yong Jiang xianran xing Jun Chen Beijing Advanced Innovation Center for Materials Genome Engineering Department of Physical ChemistryUniversity of Science and Technology BeijingBeijing 100083China School of Materials Science and Engineering University of Science and Technology BeijingBeijing 100083China State Key Laboratory for Advanced Metals and Materials University of Science and Technology BeijingBeijing 100083China NIST Center for Neutron Research National Institute of Standards and TechnologyGaithersburg MD20899-6102United States

Magnetic refrigeration based on the magnetocaloric effect(MCE)is a novel refrigeration technology that will replace traditional vapor-compression refrigeration in the *** in the performance of MCE materials is crucial for the development of magnetic refrigeration *** study presents a new method that enhances the MCE performance of(Sc,Ti)Fe_(2) via magnetic phase *** maximum magnetic entropy change induced by the coexistence of an in-plane ferromagnetic phase(FMab)and a canting antiferromagnetic phase(CAFM)in Sc_(0.3)Ti_(0.7)Fe_(2) is twice that found in other(Sc,Ti)Fe_(2 )***-temperature neutron diffraction experiments directly reveal that the large magnetic entropy change in Sc_(0.3)Ti_(0.7)Fe_(2) is dominated by the transformation from a highly ordered FMab state to a CAFM state with a lower magnetic *** magnetic phase separation is a direct transition from a higher-ordered state with a larger lattice to a lower-ordered state with a smaller lattice that induces a large magnetic order change and lattice *** combination of the metamagnetic transition and negative thermal expansion leads to enhanced *** study suggests the possibility that magnetic phase separation can be an effective approach to achieving and controlling a large MCE in magnetic materials.

关键词： Magnetocaloric effect Neutron diffraction Magnetic structure

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Carbon interstitial defects causing emission red shift in YAG:Ce phosphor:First-principles calculation

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Journal of Rare Earths 2018年第12期36卷 1239-1244页

作者： Yaling Zheng Weidong Zhuang xianran xing Ronghui Liu Yanfeng Li Yuanhong Liu Yunsheng Hu Xiaoxia Chen Lei Chen Xiaole Ma National Engineering Research Center for Rare Earth Materials General Research Institute for Nonferrous Metals and Grirem Advanced Materials Co.Ltd. Department of Physical Chemistry University of Science & Technology Beijing

Y3Al5O12:Ce3+ is the most famous phosphor material due to its excellent photolumincent ***,through first-principles calculation,the effect of carbon interstitial defects on Y3Al5O12:Ce3+phosphor was investigated. It is found that the carbon interstitials tend to occupy the next-nearest sites of Ce3+ion in Y3Al5O12:Ce3+ lattice. Specially,these interstitial defects can shorten the Ce3+-O2-bond length, leading to a larger crystal field splitting of 5 d orbital of the Ce3+atom and bigger 5 d centroid *** two factors cause the emission spectrum of Y3Al5O12(C):Ce3+red shift compared with that of Y3Al5O12:Ce3+. Moreover, with our comparison experiment, we find that the Y3Al5O12(C):Ce3+ has an obvious red shift compared with that of Y3Al5O12:Ce3+system,which is in accord with our first principles calculation. Our work systematically investigates the impact of the carbon interstitial defect on Y3Al5O12:Ce3+,and provides a new route to tune the emission spectrum in Y3Al5O12:Ce3+.

关键词： YAG:Ce Carbon interstitial defects Red shift First-principles calculation Rare earths

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Solid Solution Sm_(1+x)Ba_(2-x)Cu_3O_y and Effect of Quench Temperature on SmBa_2Cu_3O_y

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Journal of Materials Science & Technology 1994年第4期10卷 269-272页

作者： xianran xing Zhiyu QIAO Wenxia YUAN and Shoukun WEI (University of Science and Technology Beijing, Beijing, 100083, China)(To whom correspondence should be addressed)Xiaolong CHEN, Guanghui RAO and Jingkui LIANG (Institute of Physics, Chinese Academy o Univ of Science and Technology Beijing China

By X-ray powder diffraction technique and oxygen content analysis, a solid solution Sm1+xBa2-xCu3Oy has been determined in the range 0≤x≤0.4. When x<0.25. the Sm1+xBa2-xCu3Oy presents orthorhombic symmetry, and the orthorhombic-tetragonaJ transition ocCurs at x = 0.25. With the increase of x, TC decreases and finally breaks. The correlation between ox ygen content and phase structure at different quench temperatures related to Sm Ba2Cu3Oy has been investigated as well

关键词： x)Ba x)Cu3Oy and Effect of Quench Temperature on SmBa2Cu3Oy Cu Solid Solution Sm

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Thermodynamic properties of LaCrO_3

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Rare Metals 2006年第5期25卷 562-566页

作者： CHEN Zhanheng xing xianran YUAN Wenxia HUANG Xiaowei LI Hongwei School of Metallurgical and Ecological Engineering University of Science and Technology Beijing Beijing 100083 China Office of the Chinese Society of Rare Earths Beijing 100081 China National Engineering Research Center for Rare Earth Materials Beijing 100088 China

The nano powders of LaCrO3 were prepared by a sol-gel route. The heat capacity of LaCrO3 nano powders from 350 to 550 K was measured by DSC method and expressed as： Cpa2CrO3）（±0.112） = 166.844 - 8.500 ×10^-3T- 1.022×10^6T^-2 （J/（mol.K））（350-550 K）. An EMF measurement assembly was developed with CaF2 as an electrolyte for the galvanic cell. From measured EMF data of the reversible cell, （-） PL La2O3, LaF3, O2 （1 atm）lCaF2O2（1 atm）, LaF3, LaCrO3, Cr2O3, Pt（＋）, and the relevant value of Gibbs free energy, the Gibbs free energy of formation of LaCrO3 was calculated from 700 to 885 K： △G ФaLaCrO3 = -1555.364 ＋ 0.354T （kJ/mol）（700-885 K）. And the Gibbs free energy change of reaction from simple oxides La2O3 and Cr2O3 was calculated to be： AG f Oox（LaCrO3） = -94.758 ＋ 8.530×10^-2T（kJ/mol）（700-885 K）.

关键词： lanthanum chromate Gibbs free energy of formation heat capacity EMF measurement nano powder

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Neutron diffraction study on anomalous thermal expansion of CrB_(2)

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Chinese Journal of Structural Chemistry 2023年第5期42卷 8-12页

作者： Yong Xu Xin Chen Yili Cao Kun Lin Chin-Wei Wang Qiang Li Jinxia Deng Jun Miao xianran xing Beijing Advanced Innovation Center for Materials Genome Engineering Institute of Solid State ChemistryUniversity of Science and Technology BeijingBeijing100083China Neutron Group National Synchrotron Radiation Research CenterHsinchu30076TaiwanChina

Thermal expansion is an essential issue in the field of materials science and *** of anomalous thermal expansion is beneficial to controlling it and developing related ***,we report disitinctly anisotropic thermal expansion of CrB_(2)via temperature dependence of neutron diffraction,in which positive thermal expansion is observed within basal plane whereas negative thermal expansion emerges along the c ***,zero thermal expansion of unit cell volume is determined from 5 to 130 K with the coefficient of thermal expansion ofāv=0.4(1)×10^(-6)K^(-1).Magnetization measurement shows there is an antiferromagnetic-paramagnetic transition near 90 K,which may correlate to the thermal expansion *** calculations identify no chemical binding of Cr-Cr pair,implying such antiferromagnetic ordering originates from the double exchange interaction of Cr-B-Cr.

关键词： Negative thermal expansion Neutron diffraction Diboride

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