Nikita Vostrov, Isaac Martens, Mattia Colalongo, Edoardo Zatterin, Michal Ronovsky, Adrien Boulineau, Steven Leake, Xiaobo Zhu, Lianzhou Wang, Marie-Ingrid Richard, Tobias Schulli
The nanoscale mechanisms of ion deintercalation in battery cathode materials remain poorly understood, especially the relationship between crystallographic defects (dislocations, small angle grain boundaries, vacancies, etc), device performance, and durability. In this work, operando scanning X-ray diffraction microscopy (SXDM) and multi-crystal X-ray diffraction (MCXD) are used to investigate microstrain and lattice tilt inhomogeneities inside Li1 − xNi0.5Mn1.5O4 cathode particles during electrochemical cycling and their influence on the material degradation. Using these techniques, microscale lattice degradation mechanisms are investigated inside single crystals, extend it to an inter-particle scale, and correlate it with the long-term degradation of the cathode. During cycling, a crystal lattice deformation is observed, associated with phase transitions and inherent lattice defects in the measured particle. Residual misorientations are observed in the structure even after full discharge, indicating an irreversible structural change of the lattice. However, after long-term cycling such lattice misorientations together with active material dissolution are further exacerbated only in a subset of particles, suggesting high heterogeneity of degradation mechanisms between the cathode particles. Selective degradation of particles could be caused by varying crystal quality across the sample, highlighting the need for a deep understanding of defect microstructures to enable a more rational design of materials with enhanced durability.
{"title":"Plastic Deformation of LiNi0.5Mn1.5O4 Single Crystals Caused by Domain Orientation Dynamics","authors":"Nikita Vostrov, Isaac Martens, Mattia Colalongo, Edoardo Zatterin, Michal Ronovsky, Adrien Boulineau, Steven Leake, Xiaobo Zhu, Lianzhou Wang, Marie-Ingrid Richard, Tobias Schulli","doi":"10.1002/aenm.202404933","DOIUrl":"https://doi.org/10.1002/aenm.202404933","url":null,"abstract":"The nanoscale mechanisms of ion deintercalation in battery cathode materials remain poorly understood, especially the relationship between crystallographic defects (dislocations, small angle grain boundaries, vacancies, <i>etc</i>), device performance, and durability. In this work, <i>operando</i> scanning X-ray diffraction microscopy (SXDM) and multi-crystal X-ray diffraction (MCXD) are used to investigate microstrain and lattice tilt inhomogeneities inside Li<sub>1 − <i>x</i>\u0000</sub>Ni<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> cathode particles during electrochemical cycling and their influence on the material degradation. Using these techniques, microscale lattice degradation mechanisms are investigated inside single crystals, extend it to an inter-particle scale, and correlate it with the long-term degradation of the cathode. During cycling, a crystal lattice deformation is observed, associated with phase transitions and inherent lattice defects in the measured particle. Residual misorientations are observed in the structure even after full discharge, indicating an irreversible structural change of the lattice. However, after long-term cycling such lattice misorientations together with active material dissolution are further exacerbated only in a subset of particles, suggesting high heterogeneity of degradation mechanisms between the cathode particles. Selective degradation of particles could be caused by varying crystal quality across the sample, highlighting the need for a deep understanding of defect microstructures to enable a more rational design of materials with enhanced durability.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"5 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987414","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-17DOI: 10.1016/j.ensm.2025.104041
Su Hwan Jeong, In-Kyung Kim, Suyoon Eom, Hwiryeong Hwang, Young Hwa Jung, Joo-Hyung Kim
Sodium-ion batteries (SIBs) are considered promising alternatives to lithium-ion batteries (LIBs) for large-scale applications. Layered transition metal oxides are mainly used as cathode materials to enhance energy density and electrochemical performances. In this study, we compare Mn-based P2-type Na0.7Ni0.2Co0.2Mn0.6O2 (NCM) with partially Fe-substituted Na0.7Ni0.2Co0.2Mn0.5Fe0.1O2 (NCMF) via facile solid-state synthesis. Interestingly, Fe-substitution improves not only structural stability but also Na+ diffusion kinetics. It is found that the P2-O2 phase transition at high voltage region is mitigated with smaller volume change and enhanced oxygen redox reaction as demonstrated by in-situ X-ray diffraction and ex-situ X-ray photoelectron spectroscopy. In addition, density functional theory calculations exhibit that NCMF expedites Na+ diffusion and reduces the site energy difference between Naf and Nae by decreasing Na occupancy in the Naf site, which is located right below the transition metal ions. As a result, the NCMF electrode delivers a high initial energy density of 601.5 Wh kg-1 with an average discharge voltage of 3.05 V (V vs. Na+/Na). It also shows a high discharge capacity of 168.15 mAh g-1 at 0.5 C with excellent capacity retention of 68.7% after 100 cycles within a wide voltage range of 1.5-4.5 V. These findings provide a significant impact of Na site occupancy difference for improving electrochemical performance and structural stability as a rational method for the commercialization of SIBs.
{"title":"Engineering the Local Chemistry through Fe Substitution in Layered P2-Na0.7Ni0.2Co0.2Mn0.6O2 for High-Performance Sodium-Ion Batteries","authors":"Su Hwan Jeong, In-Kyung Kim, Suyoon Eom, Hwiryeong Hwang, Young Hwa Jung, Joo-Hyung Kim","doi":"10.1016/j.ensm.2025.104041","DOIUrl":"https://doi.org/10.1016/j.ensm.2025.104041","url":null,"abstract":"Sodium-ion batteries (SIBs) are considered promising alternatives to lithium-ion batteries (LIBs) for large-scale applications. Layered transition metal oxides are mainly used as cathode materials to enhance energy density and electrochemical performances. In this study, we compare Mn-based P2-type Na<sub>0.7</sub>Ni<sub>0.2</sub>Co<sub>0.2</sub>Mn<sub>0.6</sub>O<sub>2</sub> (NCM) with partially Fe-substituted Na<sub>0.7</sub>Ni<sub>0.2</sub>Co<sub>0.2</sub>Mn<sub>0.5</sub>Fe<sub>0.1</sub>O<sub>2</sub> (NCMF) via facile solid-state synthesis. Interestingly, Fe-substitution improves not only structural stability but also Na<sup>+</sup> diffusion kinetics. It is found that the P2-O2 phase transition at high voltage region is mitigated with smaller volume change and enhanced oxygen redox reaction as demonstrated by in-situ X-ray diffraction and ex-situ X-ray photoelectron spectroscopy. In addition, density functional theory calculations exhibit that NCMF expedites Na<sup>+</sup> diffusion and reduces the site energy difference between Na<sub>f</sub> and Na<sub>e</sub> by decreasing Na occupancy in the Na<sub>f</sub> site, which is located right below the transition metal ions. As a result, the NCMF electrode delivers a high initial energy density of 601.5 Wh kg<sup>-1</sup> with an average discharge voltage of 3.05 V (V vs. Na<sup>+</sup>/Na). It also shows a high discharge capacity of 168.15 mAh g<sup>-1</sup> at 0.5 C with excellent capacity retention of 68.7% after 100 cycles within a wide voltage range of 1.5-4.5 V. These findings provide a significant impact of Na site occupancy difference for improving electrochemical performance and structural stability as a rational method for the commercialization of SIBs.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"2 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987482","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Li-rich layered oxide (LRO) cathode material is utilized in anode-free Li metal batteries to provide extra Li inventory, compensating for the constant Li loss during cycling. The Li compensation mechanism of LRO in the anode-free system is elucidated by exploring the reversible/irreversible Li consumption behaviors. Moreover, the relationship between cathode areal capacity, Li inventory, and the cycling performance of the Cu||LRO cell is quantitatively analyzed. The well-designed Cu||LRO anode-free cell demonstrates 51% capacity retention after 60 cycles at a practical areal capacity of 5.0 mAh cm–2, overwhelming the 0.6% capacity retention for Cu||NCM523. Further optimization with an artificial anode protection layer and a fully fluorinated electrolyte enhances the capacity retention of Cu||LRO to 61.4% and 71.5% after 60 cycles, respectively. Combining its low initial Coulombic efficiency and high specific energy, the LRO cathode shows great prospects in the future development of high energy and long lifespan anode-free Li metal batteries.
{"title":"Regulation of Extra Li Inventory in Anode-Free Lithium Metal Batteries by Li-Rich Layered Oxide Cathode Materials","authors":"Xuejian Shi, Peiyan Sun, Chunyu Zhao, Jingyu Zhang, Jin Zhang, Teng Ma, Shenghan Wang, Chenglin Sun, Zhihui Sun, Yizhan Wang, Yingjin Wei","doi":"10.1021/acs.nanolett.4c05721","DOIUrl":"https://doi.org/10.1021/acs.nanolett.4c05721","url":null,"abstract":"Li-rich layered oxide (LRO) cathode material is utilized in anode-free Li metal batteries to provide extra Li inventory, compensating for the constant Li loss during cycling. The Li compensation mechanism of LRO in the anode-free system is elucidated by exploring the reversible/irreversible Li consumption behaviors. Moreover, the relationship between cathode areal capacity, Li inventory, and the cycling performance of the Cu||LRO cell is quantitatively analyzed. The well-designed Cu||LRO anode-free cell demonstrates 51% capacity retention after 60 cycles at a practical areal capacity of 5.0 mAh cm<sup>–2</sup>, overwhelming the 0.6% capacity retention for Cu||NCM523. Further optimization with an artificial anode protection layer and a fully fluorinated electrolyte enhances the capacity retention of Cu||LRO to 61.4% and 71.5% after 60 cycles, respectively. Combining its low initial Coulombic efficiency and high specific energy, the LRO cathode shows great prospects in the future development of high energy and long lifespan anode-free Li metal batteries.","PeriodicalId":53,"journal":{"name":"Nano Letters","volume":"31 1","pages":""},"PeriodicalIF":10.8,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987574","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Electrical control of the anomalous Hall effect (AHE) provides an important gateway to reveal and regulate topological properties of spins. However, direct, immediate electrical tuning of the AHE in materials has been elusive, unfeasible, and rarely reported. Here, we demonstrate direct, immediate, nonlinear, electric current regulation of the AHE in a single, novel, van der Waals, room-temperature, ferromagnetic, ultrathin, two-dimensional (2D) crystal for intrinsic sensitivity of nodal electronic structures induced by 2D spin-orbit coupling (SOC) in a 2D quantum limit with an ultrasmall current (∼102 A cm−2). The multivalued electrical tuning of anomalous Hall resistance (RAHE) () is up to 584% and remains 126% at room temperature. The squared correlation between RAHE and longitudinal resistance indicates an SOC-dominated Berry curvature-induced AHE. This immediate-current AHE with distinct dependence on the dimension, crystal layer, and electronic topology provides unique quantum platforms for probing the essence of the dimension and for low-power spintronics and brain-like quantum devices.
{"title":"Immediate ultrasmall current-tunable anomalous Hall effect","authors":"Li Yang, Hao Wu, Fei Guo, Gaojie Zhang, Wenfeng Zhang, Haixin Chang","doi":"10.1016/j.matt.2024.101940","DOIUrl":"https://doi.org/10.1016/j.matt.2024.101940","url":null,"abstract":"Electrical control of the anomalous Hall effect (AHE) provides an important gateway to reveal and regulate topological properties of spins. However, direct, immediate electrical tuning of the AHE in materials has been elusive, unfeasible, and rarely reported. Here, we demonstrate direct, immediate, nonlinear, electric current regulation of the AHE in a single, novel, van der Waals, room-temperature, ferromagnetic, ultrathin, two-dimensional (2D) crystal for intrinsic sensitivity of nodal electronic structures induced by 2D spin-orbit coupling (SOC) in a 2D quantum limit with an ultrasmall current (∼10<sup>2</sup> A cm<sup>−2</sup>). The multivalued electrical tuning of anomalous Hall resistance (R<sub>AHE</sub>) (<span><math><mrow is=\"true\"><mfrac is=\"true\"><mrow is=\"true\"><msub is=\"true\"><mi is=\"true\" mathvariant=\"bold-italic\">R</mi><mrow is=\"true\"><mi is=\"true\" mathvariant=\"bold-italic\">A</mi><mi is=\"true\" mathvariant=\"bold-italic\">H</mi><mi is=\"true\" mathvariant=\"bold-italic\">E</mi></mrow></msub><mn is=\"true\" mathvariant=\"bold\">1</mn></mrow><mrow is=\"true\"><msub is=\"true\"><mi is=\"true\" mathvariant=\"bold-italic\">R</mi><mrow is=\"true\"><mi is=\"true\" mathvariant=\"bold-italic\">A</mi><mi is=\"true\" mathvariant=\"bold-italic\">H</mi><mi is=\"true\" mathvariant=\"bold-italic\">E</mi></mrow></msub><mn is=\"true\" mathvariant=\"bold\">2</mn></mrow></mfrac><mo is=\"true\">∗</mo><mn is=\"true\" mathvariant=\"bold\">100</mn><mo is=\"true\">%</mo></mrow></math></span>) is up to 584% and remains 126% at room temperature. The squared correlation between R<sub>AHE</sub> and longitudinal resistance indicates an SOC-dominated Berry curvature-induced AHE. This immediate-current AHE with distinct dependence on the dimension, crystal layer, and electronic topology provides unique quantum platforms for probing the essence of the dimension and for low-power spintronics and brain-like quantum devices.","PeriodicalId":388,"journal":{"name":"Matter","volume":"120 1","pages":""},"PeriodicalIF":18.9,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987705","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ji Hu, Alexander G. Squires, Jędrzej Kondek, Arthur B. Youd, Pooja Vadhva, Michael Johnson, Partha P Paul, Philip J Withers, Marco di Michiel, Dean S Keeble, Michael Ryan Hansen, David O. Scanlon, Alexander J. E. Rettie
Lithium phosphides are an emerging class of Li+ ion conductors for solid state battery applications. Despite potentially favorable characteristics as a solid electrolyte, stoichiometric crystalline Li3AlP2 has been reported to be an ionic insulator. Using a combined computational and experimental approach, we investigate the underlying reasons for this and show that ion transport can be induced via defects and structural disorder in this material. Lithium vacancies are shown to promote diffusion, and a low barrier to Li+ hopping of 0.2-0.3 eV is revealed by both simulations and experiment. However, polycrystalline pellets exhibit low ionic conductivity (≈10−8 S cm−1) at room temperature, attributed to crystalline anisotropy and the presence of resistive grain boundaries. These aspects can be overcome in nanocrystalline Li3AlP2, where ionic conductivity values approaching 10−6 S cm−1 and low electronic conductivities are achieved. This approach, leveraging both defects and structural disorder, should have relevance to the discovery of new, or previously overlooked, ion conducting materials.
{"title":"Enabling ionic transport in Li3AlP2: the roles of defects and disorder","authors":"Ji Hu, Alexander G. Squires, Jędrzej Kondek, Arthur B. Youd, Pooja Vadhva, Michael Johnson, Partha P Paul, Philip J Withers, Marco di Michiel, Dean S Keeble, Michael Ryan Hansen, David O. Scanlon, Alexander J. E. Rettie","doi":"10.1039/d4ta04347b","DOIUrl":"https://doi.org/10.1039/d4ta04347b","url":null,"abstract":"Lithium phosphides are an emerging class of Li<small><sup>+</sup></small> ion conductors for solid state battery applications. Despite potentially favorable characteristics as a solid electrolyte, stoichiometric crystalline Li<small><sub>3</sub></small>AlP<small><sub>2</sub></small> has been reported to be an ionic insulator. Using a combined computational and experimental approach, we investigate the underlying reasons for this and show that ion transport can be induced via defects and structural disorder in this material. Lithium vacancies are shown to promote diffusion, and a low barrier to Li+ hopping of 0.2-0.3 eV is revealed by both simulations and experiment. However, polycrystalline pellets exhibit low ionic conductivity (≈10<small><sup>−8</sup></small> S cm<small><sup>−1</sup></small>) at room temperature, attributed to crystalline anisotropy and the presence of resistive grain boundaries. These aspects can be overcome in nanocrystalline Li3AlP2, where ionic conductivity values approaching 10<small><sup>−6</sup></small> S cm<small><sup>−1</sup></small> and low electronic conductivities are achieved. This approach, leveraging both defects and structural disorder, should have relevance to the discovery of new, or previously overlooked, ion conducting materials.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"30 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987863","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-17DOI: 10.1016/j.jallcom.2025.178677
, Ying Liu, Xuan Wang, Daimei Chen, Hao Ding
The superhydrophobic surface like lotus leaf had important application prospects in the field of self-cleaning of building exterior walls. However, its single function and poor UV-aging resistance severely limited its practical application. In this study, sericite, an inorganic UV-shielding material with UV absorption properties, was selected as carrier to prepared sericite-TiO2 composite particles by hydrothermal method. Then, it was modified with hexadecyltrimethoxysilane (HDTMS) and sprayed onto the substrate’s surfaces, forming a superhydrophobic coating with photocatalytic performance and UV-aging resistance. The results showed that the prepared nano-TiO2 was rutile and uniformly loaded on the sericite surface. The sericite-TiO2/HDTMS coating exhibited lotus-like superhydrophobic property with water contact angle (WCA) and water slide angle (WSA) of 154.7° and 2.1°, respectively. The coating also showed photocatalytic performance, and 35.8% of 10 ppm methyl orange solution can be degraded under UV light in 50 min. Due to the fact that sericite was an inorganic UV-shielding agent, the as-prepared coating showed UV-aging property. After UV irradiation for 40 h, WCA of the surface still approach 150°. The sericite-TiO2/HDTMS coating not only had self-cleaning performance and UV-aging property, but also the potential for practical applications.
{"title":"Fabrication of sericite-TiO2/HDTMS superhydrophobic self-cleaning coatings by hydrothermal method","authors":", Ying Liu, Xuan Wang, Daimei Chen, Hao Ding","doi":"10.1016/j.jallcom.2025.178677","DOIUrl":"https://doi.org/10.1016/j.jallcom.2025.178677","url":null,"abstract":"The superhydrophobic surface like lotus leaf had important application prospects in the field of self-cleaning of building exterior walls. However, its single function and poor UV-aging resistance severely limited its practical application. In this study, sericite, an inorganic UV-shielding material with UV absorption properties, was selected as carrier to prepared sericite-TiO<sub>2</sub> composite particles by hydrothermal method. Then, it was modified with hexadecyltrimethoxysilane (HDTMS) and sprayed onto the substrate’s surfaces, forming a superhydrophobic coating with photocatalytic performance and UV-aging resistance. The results showed that the prepared nano-TiO<sub>2</sub> was rutile and uniformly loaded on the sericite surface. The sericite-TiO<sub>2</sub>/HDTMS coating exhibited lotus-like superhydrophobic property with water contact angle (WCA) and water slide angle (WSA) of 154.7° and 2.1°, respectively. The coating also showed photocatalytic performance, and 35.8% of 10 ppm methyl orange solution can be degraded under UV light in 50<!-- --> <!-- -->min. Due to the fact that sericite was an inorganic UV-shielding agent, the as-prepared coating showed UV-aging property. After UV irradiation for 40<!-- --> <!-- -->h, WCA of the surface still approach 150°. The sericite-TiO<sub>2</sub>/HDTMS coating not only had self-cleaning performance and UV-aging property, but also the potential for practical applications.","PeriodicalId":344,"journal":{"name":"Journal of Alloys and Compounds","volume":"8 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987967","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Perovskite materials are currently widely used in 5 G applications. We have examined a series of lead-free (Ba1-xCax)(Ti0.9Sn0.1)O3 (BCTS) ceramic samples (x which were synthesized using the conventional method. A systematic study of the structural, dielectric, shielding, and ferroelectric properties of Ca-doped BCTS ceramics was carried out. Rietveld refinement confirmed that BCTS samples had multiple phases with no other impurity phases. The crystallite size, average grain size, surface roughness, and structural mode of vibrations were determined by XRD, FESEM, and RAMAN analysis. The dielectric and conductivity properties were studied as a function of temperature (25 - 300and frequency range of (1 kHz - 2 MHz). The maximum dielectric constant value of ~ 13,800 was observed for the composition x = 0.01 at 1 kHz. Conductivity analysis was done by using Jonscher’s universal power law (JPL) and Arrhenius equations. The ferroelectric properties of BCTS ceramic samples were investigated and the value of polarization was maximum for x = 0.01 (Ps = 11.24 µC/cm2). Additionally, the shielding properties (S11 and S12 parameters) of BCTS ceramic pellets were examined in the frequency range of 12.4-18 GHz using a Vector Network Analyzer (VNA). The maximum total effective shielding value of 52 dB for BCTS ceramic pellets for x = 0.05 indicated good shielding behavior for high-frequency EMI shielding applications.
{"title":"Structural, Dielectric & Ferroelectric study in lead-free Ba(Ti0.9Sn0.1)O3 ceramics for EMI shielding applications","authors":"Arpita Priyadarsini Dikshit, Dibyaranjan Das, Ritu Roumya Samal, Prafulla Kumar Dash, Kajal Parashar, S.K.S. Parashar","doi":"10.1016/j.jallcom.2025.178687","DOIUrl":"https://doi.org/10.1016/j.jallcom.2025.178687","url":null,"abstract":"Perovskite materials are currently widely used in 5<!-- --> <!-- -->G applications. We have examined a series of lead-free (Ba<sub>1-x</sub>Ca<sub>x</sub>)(Ti<sub>0.9</sub>Sn<sub>0.1</sub>)O<sub>3</sub> (BCTS) ceramic samples (x<span><math><mspace is=\"true\" width=\"1em\"></mspace><mo is=\"true\" linebreak=\"goodbreak\" linebreakstyle=\"after\">=</mo><mn is=\"true\">0</mn><mo is=\"true\">,</mo><mspace is=\"true\" width=\"0.25em\"></mspace><mn is=\"true\">0.01</mn><mo is=\"true\">,</mo><mspace is=\"true\" width=\"0.25em\"></mspace><mn is=\"true\">0.05</mn><mo is=\"true\">,</mo><mspace is=\"true\" width=\"0.25em\"></mspace><mn is=\"true\">0.1</mn><mo is=\"true\" stretchy=\"false\">)</mo></math></span> which were synthesized using the conventional method. A systematic study of the structural, dielectric, shielding, and ferroelectric properties of Ca-doped BCTS ceramics was carried out. Rietveld refinement confirmed that BCTS samples had multiple phases with no other impurity phases. The crystallite size, average grain size, surface roughness, and structural mode of vibrations were determined by XRD, FESEM, and RAMAN analysis. The dielectric and conductivity properties were studied as a function of temperature (25 - 300<span><math><mspace is=\"true\" width=\"1em\"></mspace><mi is=\"true\">℃</mi><mo is=\"true\" stretchy=\"false\">)</mo><mspace is=\"true\" width=\"0.25em\"></mspace></math></span>and frequency range of (1<!-- --> <!-- -->kHz - 2<!-- --> <!-- -->MHz). The maximum dielectric constant value of ~ 13,800 was observed for the composition x = 0.01 at 1<!-- --> <!-- -->kHz. Conductivity analysis was done by using Jonscher’s universal power law (JPL) and Arrhenius equations. The ferroelectric properties of BCTS ceramic samples were investigated and the value of polarization wa<sub><em>s</em></sub> maximum for x = 0.01 (<em>P</em><sub><em>s</em></sub> = 11.24 <em>µC/cm</em><sup><em>2</em></sup>). Additionally, the shielding properties (S<sub>11</sub> and S<sub>12</sub> parameters) of BCTS ceramic pellets were examined in the frequency range of 12.4-18<!-- --> <!-- -->GHz using a Vector Network Analyzer (VNA). The maximum total effective shielding value of 52<!-- --> <!-- -->dB for BCTS ceramic pellets for x = 0.05 indicated good shielding behavior for high-frequency EMI shielding applications.","PeriodicalId":344,"journal":{"name":"Journal of Alloys and Compounds","volume":"45 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987969","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-17DOI: 10.1016/j.jallcom.2025.178709
Cong Peng, Xiaoxia Chen, Qingan Zhang
As a hydrogen storage material, magnesium hydride (MgH2) has attracted global attention. Notwithstanding its high capacity, the utilization of MgH2 is severely hampered by slow dehydrogenation rates. To accelerate hydrogen desorption of MgH2, herein, a nanoscale Nb2O5-C/Ti3C2Tx composite catalyst has been synthesized via a fast Joule heating method. After incorporating this catalyst into MgH2 through mechanical milling, the as-prepared MgH2–10 wt% Nb2O5-C/Ti3C2Tx sample displays the enhanced dehydrogenation kinetics with activation energy of 62.5 kJ mol–1 and excellent cyclic durability (99.3% after 50 cycles). The performance improvement is attributed not only to the synergetic catalysis of multivalent Ti and Nb species but also to the hindering role of carbon nanoparticles and Ti3C2Tx nanosheets in powder agglomeration. The strategy reported here offers innovative solutions to developing highly efficient catalytic agents for hydrogen desorption of MgH2-based composites.
{"title":"Enhancing dehydrogenation kinetics of MgH2 through doping with the Nb2O5-C/Ti3C2Tx catalyst synthesized by fast Joule heating","authors":"Cong Peng, Xiaoxia Chen, Qingan Zhang","doi":"10.1016/j.jallcom.2025.178709","DOIUrl":"https://doi.org/10.1016/j.jallcom.2025.178709","url":null,"abstract":"As a hydrogen storage material, magnesium hydride (MgH<sub>2</sub>) has attracted global attention. Notwithstanding its high capacity, the utilization of MgH<sub>2</sub> is severely hampered by slow dehydrogenation rates. To accelerate hydrogen desorption of MgH<sub>2</sub>, herein, a nanoscale Nb<sub>2</sub>O<sub>5</sub>-C/Ti<sub>3</sub>C<sub>2</sub>T<sub><em>x</em></sub> composite catalyst has been synthesized via a fast Joule heating method. After incorporating this catalyst into MgH<sub>2</sub> through mechanical milling, the as-prepared MgH<sub>2</sub>–10<!-- --> <!-- -->wt% Nb<sub>2</sub>O<sub>5</sub>-C/Ti<sub>3</sub>C<sub>2</sub>T<sub><em>x</em></sub> sample displays the enhanced dehydrogenation kinetics with activation energy of 62.5<!-- --> <!-- -->kJ<!-- --> <!-- -->mol<sup>–1</sup> and excellent cyclic durability (99.3% after 50 cycles). The performance improvement is attributed not only to the synergetic catalysis of multivalent Ti and Nb species but also to the hindering role of carbon nanoparticles and Ti<sub>3</sub>C<sub>2</sub>T<sub><em>x</em></sub> nanosheets in powder agglomeration. The strategy reported here offers innovative solutions to developing highly efficient catalytic agents for hydrogen desorption of MgH<sub>2</sub>-based composites.","PeriodicalId":344,"journal":{"name":"Journal of Alloys and Compounds","volume":"6 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988019","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yi Song, Yu Liu, Wenwei Liu, Zhiyi Zhao, Xiaoqiong Liu, Ying Xu, Tao Li
Copper–tantalum (Cu–Ta) immiscible alloy nanoparticles (NPs) have been the subject of extensive research in the field of structural materials, due to their exceptional nanostructural stability and high-temperature creep properties. However, Cu is also a highly active oxidation catalyst due to its abundant valence changes. In this study, we have for the first time obtained homogeneous CuxTa1–x (x = 0.5, 0.7, 0.9, 1) nanoparticles by wet coreduction with an average particle size of approximately 30 nm. Testing verified all the CuxTa1–x/TiO2 (x = 0.5, 0.7, 0.9) showed higher CO oxidation activity than Cu/TiO2, with Cu0.7Ta0.3/TiO2 exhibiting the most promising performance. The temperature-programmed reduction with hydrogen demonstrated that Cu0.7Ta0.3/TiO2 exhibits enhanced redox properties. While kinetic studies indicated that the reaction of the Cu0.7Ta0.3/TiO2 catalyst followed the Langmuir–Hinshelwood mechanism, in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) verified the introduction of Ta induced the generation of bicarbonate as an intermediate product and increased the adsorption capacity of Cu+ on CO in the catalyst, which facilitated the reaction of surface adsorbed CO with oxygen and led to the enhanced CO oxidation activity.
{"title":"Enhancing the CO Oxidation Performance of Copper by Alloying with Immiscible Tantalum","authors":"Yi Song, Yu Liu, Wenwei Liu, Zhiyi Zhao, Xiaoqiong Liu, Ying Xu, Tao Li","doi":"10.1021/acsami.4c19374","DOIUrl":"https://doi.org/10.1021/acsami.4c19374","url":null,"abstract":"Copper–tantalum (Cu–Ta) immiscible alloy nanoparticles (NPs) have been the subject of extensive research in the field of structural materials, due to their exceptional nanostructural stability and high-temperature creep properties. However, Cu is also a highly active oxidation catalyst due to its abundant valence changes. In this study, we have for the first time obtained homogeneous Cu<sub><i>x</i></sub>Ta<sub>1–<i>x</i></sub> (<i>x</i> = 0.5, 0.7, 0.9, 1) nanoparticles by wet coreduction with an average particle size of approximately 30 nm. Testing verified all the Cu<sub><i>x</i></sub>Ta<sub>1–<i>x</i></sub>/TiO<sub>2</sub> (<i>x</i> = 0.5, 0.7, 0.9) showed higher CO oxidation activity than Cu/TiO<sub>2</sub>, with Cu<sub>0.7</sub>Ta<sub>0.3</sub>/TiO<sub>2</sub> exhibiting the most promising performance. The temperature-programmed reduction with hydrogen demonstrated that Cu<sub>0.7</sub>Ta<sub>0.3</sub>/TiO<sub>2</sub> exhibits enhanced redox properties. While kinetic studies indicated that the reaction of the Cu<sub>0.7</sub>Ta<sub>0.3</sub>/TiO<sub>2</sub> catalyst followed the Langmuir–Hinshelwood mechanism, in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) verified the introduction of Ta induced the generation of bicarbonate as an intermediate product and increased the adsorption capacity of Cu<sup>+</sup> on CO in the catalyst, which facilitated the reaction of surface adsorbed CO with oxygen and led to the enhanced CO oxidation activity.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"30 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988222","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Suchhanda Swain, Amit Kumar Swain, Bikash Kumar Kumar Jena
The status of investigations on metal-air batteries (MABs) is yet in the unfledged stage, so the full sustainability of real-life applications cannot be predicted. A potential MAB system needs to be designed to avoid the phenomena instigating the premature failure of the cell. This review primarily addresses the toolbox for accumulating Zn and Al-air batteries for the enumerated deliberations, emphasizing separator-like polymeric anion exchange membrane systems. The physicochemical characteristics of the membrane structure stimulate the overall performance, stability, safety, cyclic efficiency, durability, and scalability of the battery device. Nevertheless, developing relevant membranes has not yet received the recognition it deserves. The main panorama in this review is the rational delineation of anion exchange polymer membranes (AEPMs) as a separator with a rich set of opportunities. Some promising membrane-forming materials, including different polymers and nanofillers, are investigated. Information has been presented on the current issues and challenges that restrict the full implementation of metallic anode compartments, specifically zinc and aluminum anodes in the case of ZAB and AAB systems, respectively. A section dedicated to the influence of separators on addressing the issues related to the anode side of the battery systems has been summarized here. Finally, the outlooks on the scalability, environmental impact, and future advancement of the AEPM as a potential separator toward practical large-scale battery applications are recapitulated.
{"title":"Anion Exchange Polymer Membrane (AEPM)-based separators: An unexplored frontier for ZAB and AAB systems","authors":"Suchhanda Swain, Amit Kumar Swain, Bikash Kumar Kumar Jena","doi":"10.1039/d4ta07636b","DOIUrl":"https://doi.org/10.1039/d4ta07636b","url":null,"abstract":"The status of investigations on metal-air batteries (MABs) is yet in the unfledged stage, so the full sustainability of real-life applications cannot be predicted. A potential MAB system needs to be designed to avoid the phenomena instigating the premature failure of the cell. This review primarily addresses the toolbox for accumulating Zn and Al-air batteries for the enumerated deliberations, emphasizing separator-like polymeric anion exchange membrane systems. The physicochemical characteristics of the membrane structure stimulate the overall performance, stability, safety, cyclic efficiency, durability, and scalability of the battery device. Nevertheless, developing relevant membranes has not yet received the recognition it deserves. The main panorama in this review is the rational delineation of anion exchange polymer membranes (AEPMs) as a separator with a rich set of opportunities. Some promising membrane-forming materials, including different polymers and nanofillers, are investigated. Information has been presented on the current issues and challenges that restrict the full implementation of metallic anode compartments, specifically zinc and aluminum anodes in the case of ZAB and AAB systems, respectively. A section dedicated to the influence of separators on addressing the issues related to the anode side of the battery systems has been summarized here. Finally, the outlooks on the scalability, environmental impact, and future advancement of the AEPM as a potential separator toward practical large-scale battery applications are recapitulated.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"11 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988322","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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