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Dual-phase medium-entropy diboride–carbide ceramics with metal element exchange during sintering

Journal of Advanced ceramics 2025年第1期14卷 91-100页

作者： Pai Peng Ji-Xuan Liu Xiao-Ting Xin Weichao Bao Yongcheng Liang Fangfang Xu Guo-Jun Zhang State Key Laboratory of Advanced Fiber Materials Institute of Functional MaterialsCollege of Materials Science and EngineeringCollege of PhysicsDonghua UniversityShanghai 201620China State Key Laboratory of High Performance Ceramics and Superfine Microstructure Shanghai Institute of CeramicsChinese Academy of SciencesShanghai 200050China

Multiphase composition design is a strategy for optimizing the microstructures and properties of ceramic materials through mutual inhibition of grain growth, complementary property improvement, or even mutually reinforcing effects. More interesting phenomena can be expected if chemical interactions between the constituent phases exist. In this study, spark plasma sintering was used to prepare fully dense dual-phase (Zr,Hf,Ta)B_(2)–(Zr,Hf,Ta)C ceramics from self-synthesized equimolar medium-entropy diboride and carbide powders. The obtained ceramics were composed of two distinct solid solution phases, the Zr-rich diboride phase and the Ta-rich carbide phase, indicating that metal element exchange occurred between the starting equimolar medium-entropy diboride and carbide phases during sintering. Owing to the mutual grain-boundary pinning effect, fine-grained dual-phase ceramics were obtained. The chemical driving force originating from metal element exchange during the sintering process is considered to promote the densification process of the ceramics. The metal element exchange between the medium-entropy diboride and carbide phases significantly increased the Young’s modulus of the dual-phase ceramics. The dual-phase medium-entropy 50 vol% (Zr,Hf,Ta)B_(2)–50 vol% (Zr,Hf,Ta)C ceramics with the smallest grain size exhibited the highest hardness of 22.4±0.2 GPa. It is inferred that optimized comprehensive properties or performance of dual-phase high-entropy or medium-entropy ceramics of diborides and carbides can be achieved by adjusting both the volume content and the metal element composition of the corresponding starting powders of diborides and carbides.

关键词： medium-entropy diboride medium-entropy carbide dual-phase medium-entropy ceramics metal element exchange densification mechanical properties

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Reversible Li plating regulation on graphite anode through a barium sulfate nanofibers-based dielectric separator for fast charging and high-safety lithium-ion battery

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Journal of Energy Chemistry 2025年第2期101卷 511-523,I0011页

作者： Yaxin Zhang Long Cheng Ying-Jie Zhu Jin Wu Han-Ping Yu Sida Xie Dandan Li Zhaohui Wang Heng Li State Key Laboratory of High Performance Ceramics and Superfine Microstructure Shanghai Institute of CeramicsChinese Academy of SciencesShanghai 200050China College of Materials Science and Engineering Hunan UniversityChangsha 410082HunanChina Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of SciencesBeijing 100049China

Poor Li plating reversibility and high thermal runaway risks are key challenges for fast charging lithiumion batteries with graphite ***,a dielectric and fire-resistant separator based on hybrid nanofibers of barium sulfate(BS)and bacterial cellulose(BC)is developed to synchronously enhance the battery's fast charging and thermal-safety *** regulation mechanism of the dielectric BS/BC separator in enhancing the Li^(+)ion transport and Li plating reversibility is revealed.(1)The Max-Wagner polarization electric field of the dielectric BS/BC separator can accelerate the desolvation of solvated Li^(+)ions,enhancing their transport kinetics.(2)Moreover,due to the charge balancing effect,the dielectric BS/BC separator homogenizes the electric field/Li^(+)ion flux at the graphite anode-separator interface,facilitating uniform Li plating and suppressing Li dendrite ***,the fast-charge graphite anode with the BS/BC separator shows higher Coulombic efficiency(99.0%vs.96.9%)and longer cycling lifespan(100 cycles vs.59 cycles)than that with the polypropylene(PP)separator in the constantlithiation cycling test at 2 mA cm^(-2).The high-loading LiFePO4(15.5 mg cm^(-2))//graphite(7.5 mg cm^(-2))full cell with the BS/BC separator exhibits excellent fast charging performance,retaining 70%of its capacity after 500 cycles at a high rate of 2C,which is significantly better than that of the cell with the PP separator(retaining only 27%of its capacity after 500 cycles).More importantly,the thermally stable BS/BC separator effectively elevates the critical temperature and reduces the heat release rate during thermal runaway,thereby significantly enhancing the battery's safety.

关键词： Fast charging Lithium-ion battery Graphite anode Separator lon transport

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Microwave-induced surface amorphization of Cu_(2)(OH)_(2)CO_(3) catalyst promotes multi-carbon products selectivity of CO_(2) electroreduction

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Science China Chemistry 2025年第4期68卷 1597-1607页

作者： Jie Wang Min Wang Yang Wang Zixuan Wei Xin He Haojie Zang Xixiong Jin Lingxia Zhang State Key Lab of High Performance Ceramics and Superfine Microstructure Shanghai Institute of CeramicsChinese Academy of SciencesShanghai 200050China Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of SciencesBeijing 100049China School of Chemistry and Materials Science Hangzhou Institute for Advanced StudyUniversity of Chinese Academy of Sciences Hangzhou 310024China

For CO_(2) electroreduction;efficient catalysts with superior selectivity toward multi-carbon(C_(2+))products(such as C_(2)H_(4);C_(2)H_(5)OH;etc.)are intensely *** Cu-based catalysts show appealing performance on the crucial C–C coupling;but their synthesis procedures are complicated and their actual mechanisms are still *** this work;surface amorphization has been implemented on Cu_(2)(OH)_(2)CO_(3) catalysts by a very simple microwave-induction method;improving the Faradaic efficiency for C_(2+)products(FE_(C_(2+)))up to 86%(increased by~26%than that on Cu_(2)(OH)_(2)CO_(3))at a partial current density of 258 mA cm^(-2);and a high FEC_(2+)of 75%at 500 m A cm^(-2)in a flow ***;the catalyst exhibits good *** situ investigations disclose that the amorphous surface optimizes the adsorption state(binding mode and coverage)of key intermediate*CO and stabilizes Cu^(+)pieces;facilitating the dimerization of*CO into*OCCO and hydrogenation to*OC_(2)H_(5);ultimately achieving high yields of C_(2+)*** work highlights a simple microwave approach for surface amorphization and the roles of amorphous features in CO_(2) reduction to C_(2+)products;which could be valuable references for designing highperformance catalysts for CO_(2) electroreduction.

关键词： microwave treatment amorphous surface Cu-based catalysts electrocatalytic CO reduction multi-carbon products

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Wafer‑Scale Ag_(2)S‑Based Memristive Crossbar Arrays with Ultra‑Low Switching‑Energies Reaching Biological Synapses

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Nano-Micro Letters 2025年第3期17卷 328-339页

作者： Yuan Zhu Tomas Nyberg Leif Nyholm Daniel Primetzhofer Xun Shi Zhen Zhang Division of Solid‑State Electronics Department of Electrical EngineeringUppsala University75121 UppsalaSweden Department of Chemistry Uppsala UniversityUppsalaSweden Department of Physics and Astronomy Uppsala UniversityUppsalaSweden State Key Laboratory of High Performance Ceramics and Superfine Microstructure Shanghai Institute of CeramicsChinese Academy of SciencesShanghai 200050People’s Republic of China

Memristive crossbar arrays(MCAs)offer parallel data storage and processing for energy-efficient neuromorphic ***,most wafer-scale MCAs that are compatible with complementary metal-oxide-semiconductor(CMOS)technology still suffer from substantially larger energy consumption than biological synapses,due to the slow kinetics of forming conductive paths inside the memristive *** we report wafer-scale Ag_(2)S-based MCAs realized using CMOS-compatible processes at temperatures below 160℃.Ag_(2)S electrolytes supply highly mobile Ag+ions,and provide the Ag/Ag_(2)S interface with low silver nucleation barrier to form silver filaments at low energy *** further enhancing Ag+migration in Ag_(2)S electrolytes via microstructure modulation,the integrated memristors exhibit a record low threshold of approximately−0.1 V,and demonstrate ultra-low switching-energies reaching femtojoule values as observed in biological *** low-temperature process also enables MCA integration on polyimide substrates for applications in flexible ***,the intrinsic nonidealities of the memristive units for deep learning can be compensated by employing an advanced training *** impressive accuracy of 92.6%in image recognition simulations is demonstrated with the MCAs after the *** demonstrated MCAs provide a promising device option for neuromorphic computing with ultra-high energy-efficiency.

关键词： Wafer-scale Ag_(2)S films Reactive sputter Silver nucleation Ag^(+)migration Energy-efficient neuromorphic computing

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Integrated multi-scale synchrotron radiation-technology studies on AlPO_(4)-coating modification mechanism in lithium-rich manganese-based cathode

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Nuclear Science and Techniques 2025年第5期36卷 30-42页

作者： Zhong-Qin Dai Huan Chen Zhao-Yin Wen School of Physical Science and Technology ShanghaiTech UniversityShanghai 201210China The State Key Lab High-Performance Ceram&Superfine Shanghai Institute of CeramicsChinese Academy of SciencesShanghai 200050China University of Chinese Academy of Science Beijing 100049China

Lithium-and manganese-rich(LMR)oxide cathode materials are among the most attractive candidates for next-generation energy-storage materials owing to their anomalous ***,severe Mn dissolution that occurs during long-term cycling,which leads to capacity loss,hinders their application *** this study,nanoscale AlPO_(4)-coated Li_(1.2)Ni_(0.13)Co_(0.13)Mn_(0.54)O_(2)(LMR@APO)with significantly enhanced electrochemical performance is successfully synthesized using a simple and effective sol–gel method to mitigate Mn dissolution and suppress local structural distortion at high *** of the complex evolution of the structure and oxidation state of LMR materials during electrochemical cycling,observing and analyzing them using traditional single characterization methods may be ***,we combine various synchrotron-based characterization techniques to conduct a detailed analysis of the electronic and coordination structures of the cathode material from the surface to the ***-based hard and soft X-ray spectroscopies are integrated to investigate the differences in O and Mn evolution between the surfaces and bulk of the *** synchrotron-based transmission X-ray microscopy combined with X-ray near-edge absorption-structure technology is utilized to visualize the two-dimensional nanometer-scale reactivity of the LMR *** AlPO_(4)-coating layer can stabilize the surface structure of the LMR material,effectively alleviating irreversible oxygen release on the surface and preventing the dissolution of Mn^(2+)at the interface caused by side reactions after a long ***,the spatial reaction uniformity of Mn is enhanced by the AlPO_(4)-coating layer,and rapid capacity decay caused by Mn deactivation is *** AlPO_(4)-coating method is a facile modification strategy for high-performance LMR materials.

关键词： Synchrotron radiation X-ray absorption fine structure X-ray imaging Amorphous coating layer Lithium-and manganese-rich(LMR)cathode

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Optical characteristics and surface dendritic growth of Nd,Y:CaF2 crystals irradiated by high-energy He ions

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ceramics International 2025年第12期51卷 16551-16558页

作者： Lu, Zhuowei Zhang, Zhonghan Wang, Xu Kou, Huamin Jiang, Dapeng Wang, Jingya Zhang, Bo Wu, Anhua Su, Liangbi State Key Laboratory of High Performance Ceramics and Superfine Microstructure Shanghai Institute of Ceramics Chinese Academy of Sciences Shanghai201899 China Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of Sciences Beijing100049 China School of Materials and Chemistry University of Shanghai for Science and Technology Shanghai200093 China

This study aims to investigate the various responses of the optical characteristics to He-ion irradiation at different fluences and energies in Nd,Y:CaF2 crystals. Through optical absorption and photoluminescence spectra, we observe that electrons excited by He-ion irradiation are trapped by anionic vacancies, He ions and Nd3+ to form F-centers, He atoms and Nd2+, respectively. At an energy of 5 MeV, F-centers decrease with increasing fluence, whereas at a fluence of 1 × 1013 ions/cm2, increasing the energy promotes Nd2+ formation, and a further increase in the fluence based on an energy of 16 MeV can significantly promote the production of Nd2+. After the irradiation, the electrons from F-centers are also captured by Nd3+, leading to the decay of F-centers and an increase in Nd2+ with time. In addition, the growth of CaF2 dendrites with multiple morphologies on the surface by high-energy irradiation is observed. It is explained by the surface recrystallization between the escape of F and surface metallization due to high-energy irradiation. This research provides significant insights into the irradiation conditions modulating defect generation and evolution, as well as laying the groundwork for future applications of radiation-exposed crystals as radiation dosimeters and lasers. © 2024

关键词： Ion bombardment

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Exceptional room-temperature processability of Ag2(S,Te) by iterative sublattice amorphization

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Science China Materials 2025年 1-3页

作者： Wang, Yumeng Qiu, Pengfei Shi, Xun State Key Laboratory of High Performance Ceramics and Superfine Microstructure Shanghai Institute of Ceramics Chinese Academy of Sciences Shanghai200050 China Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of Sciences Beijing100049 China

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Insights into the intelligent multi-field response of nonlinear permittivity in the canonical antiferroelectric ceramics

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材料科学技术（英文版） 2025年第1期204卷 10-17页

作者： Yizheng Bao Xuefeng Chen Kunjie Lou Canyu Che Fei Cao Shiguang Yan Genshui Wang Key Laboratory of Inorganic Functional Materials and Devices Shanghai Institute of CeramicsChinese Academy of SciencesShanghai 201800China State Key Laboratory of High-Performance Ceramics and Superfine Microstructure Shanghai Institute of CeramicsChinese Academy of SciencesShanghai 200050China Key Laboratory of Inorganic Functional Materials and Devices Shanghai Institute of CeramicsChinese Academy of SciencesShanghai 201800China School of Chemistry and Materials Science.Hangzhou Institute for Advanced Study University of Chinese Academy of SciencesHangzhou 310024China Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of SciencesBeijing 100049China Key Laboratory of Inorganic Functional Materials and Devices Shanghai Institute of CeramicsChinese Academy of SciencesShanghai 201800China State Key Laboratory of High-Performance Ceramics and Superfine Microstructure Shanghai Institute of CeramicsChinese Academy of SciencesShanghai 200050China School of Chemistry and Materials Science.Hangzhou Institute for Advanced Study University of Chinese Academy of SciencesHangzhou 310024China Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of SciencesBeijing 100049China

Due to the atomic-level centrosymmetric spontaneous polarization,antiferroelectric materials exhibit a sensitively nonlinear capacitive response to plural physic fields(mainly electric field and temperature)in a certain range,consequently leading to some superb material properties,e.g.,ripple suppression,elec-trocaloric cooling,and dielectric energy ***,there are many cognitive blanks about how this exotic multi-field relation ε(EDC,T)is influenced and manipulated via microscopic structures in the *** this work,the classic antiferroelectric ceramics PLZT were selected to see this intelligent effect,based on a quad-parameterized ε(EDC)relation on the dependence of T.ε relations were studied under different material compositions,temperature,frequency,AC electric field,and DC electric field,re-vealing lattice/domain structure evolution and the underlying *** inherent phase stability,introduced random field,and hierarchical hysteresis states were found to co-dominate this multi-field nonlinear *** work would not only contribute to future progress in the current applications(ripple suppression/electrocaloric cooling/dielectric energy storage)but imply the possibility of co-sensing temperature and electric potential simply and smartly.

关键词： Antiferroelectric ceramic Nonlinear permittivity Positive bias-field permittivity Multi-field response Temperature-electric potential co-sensing

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Long term ablation behavior and mechanisms of Y2O3 reinforced Cf/HfB2-SiC composites

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ceramics International 2025年第13期51卷 18296-18304页

作者： Zhang, Fan Ni, Dewei Chen, Bowen Cai, Feiyan Wang, Hongda Gao, Le He, Ping Ding, Yusheng Dong, Shaoming State Key Laboratory of High-Performance Ceramics & Superfine Microstructure Shanghai Institute of Ceramics Chinese Academy of Sciences Shanghai200050 China Structural Ceramics and Composites Engineering Research Center Shanghai Institute of Ceramics Chinese Academy of Sciences Shanghai200050 China University of Chinese Academy of Sciences Beijing100049 China Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China

Ultrahigh temperature and long-term ablation-resistant properties are critical and challenging for the utilization of materials as the thermal components of hypersonic vehicles. In this work, Y2O3 reinforced Cf/HfB2-SiC composites are designed and fabricated, which present superior ablation resistance with a mass recession rate of 2.10 mg/s and linear recession rate of 0.67 μm/s (with 3 wt% Y2O3 addition) under long term ablation at a heat flux of 5.5 MW/m2 (up to ∼ 2700 °C) for 300 s. The long-term ablation mechanisms of the composites are studied and revealed with the help of a detailed microstructure analysis and thermodynamic considerations. It is indicated that Y2O3 reacts with both HfO2 and SiO2, leading to the formation of a stable oxide layer with small HfO2-based grains skeleton dispersed in HfO2-Y2O3-SiO2 glassy phase, subsequently improving the ablation-resistant performance of the composites. This work inspires new strategies for further optimization of ablation resistance of ultra-high temperature ceramic matrix composites. © 2025 Elsevier Ltd and Techna Group S.r.l.

关键词： Reinforcement

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Effect of sintering temperature on electrical resistivity and mechanical properties of Si3N4-TiC0.5N0.5 composite ceramics

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ceramics International 2025年

作者： Zhu, Ming Xia, Yongfeng Yao, Dongxu Zhao, Jun Zeng, Yu-Ping State Key Laboratory of High Performance Ceramics and Superfine Microstructure Shanghai Institute of Ceramics Chinese Academy of Sciences Shanghai200050 China

Si3N4-TiC0.5N0.5 composites with low electrical resistivity and great mechanical properties were prepared via hot pressed sintering. The effects of sintering temperature (1500–1800 °C) on phase composition, microstructures, electrical resistivity and mechanical properties were systematically investigated. Percolation effects were observed in all samples, but variations in microstructures resulted in the differences in electrical resistivity. The sample sintered at 1600 °C showed the highest resistivity of 2798.44 Ω cm, which was attributed to the Si3N4 and TiC0.5N0.5 grains being fully immersed in the liquid-phase environment. With the increase of sintering temperature, the increased connectivity of TiC0.5N0.5 and the thinner amorphous layer between Si3N4-TiC0.5N0.5 grain boundary resulted in the decrease of resistivity. As the sintering temperature rose to 1800 °C, the amorphous layer disappeared, resulting in the resistivity greatly reduced to 18.9 Ω cm. The sample sintered at 1800 °C also showed great mechanical properties, with the flexural strength, elastic modulus, fracture toughness and hardness of 750 MPa, 340 GPa, 6.94 MPa m1/2 and 14.8 GPa, respectively. On the whole, the electrical resistivity and mechanical properties of Si3N4-TiC0.5N0.5 composites had been tailored by adjusting the microstructure, which made it possible to be applied in the electrical devices. © 2025 Elsevier Ltd and Techna Group S.r.l.

关键词： Fracture toughness

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