Siqing He, Changhao Xiang, Wei Liu, Songting Liang, Rui Zhang, Weikun Chen, Bin Zhao, Jun Yuan, Yingping Zou
π-linked organic small molecular acceptor materials, (also known as A-π-A quasi-macromolecule (QM) acceptors) have attracted considerable attention in organic solar cells (OSCs) due to their well-defined structures, batch reproducibility, improved morphology, enhanced stability etc. Altering the π bridge unit is a simple yet effective way to modulate molecular configuration and packing motifs, and thus affecting the efficiency of the resulting OSCs. Herein, we synthesized three A-π-A QM acceptors, QM-1T, QM-2T and QM-3T, with different conjugation length of π bridge units (thiophene, bithiophene and terthiophene) and studied exquisitely controlling the molecular size to influence the active-layer morphology and device performance. The theoretical calculations and experimental characterization results show that QM-2T exhibits an increased absorption, upshifted LUMO level and more ordered stacking pattern thanks to the relatively suitable π bridge length. The well-controlled morphology in the blend of PM6:QM-2T also results in the much-improved and balanced electron and hole mobility. Accordingly, QM-2T-based OSC achieves a high open circuit voltage of 0.94 V without sacrificing short circuit current density, resulting for a higher device efficiency of 17.86% than QM-1T and QM-3T. These results highlight the significance of molecular geometric design by featuring conjugated π bridge lengths to achieve high-performance OSCs.
{"title":"A-π-A type quasi-macromolecular acceptors with molecular conjugation length control strategy for high-performance organic solar cells","authors":"Siqing He, Changhao Xiang, Wei Liu, Songting Liang, Rui Zhang, Weikun Chen, Bin Zhao, Jun Yuan, Yingping Zou","doi":"10.1039/d4ta05543h","DOIUrl":"https://doi.org/10.1039/d4ta05543h","url":null,"abstract":"π-linked organic small molecular acceptor materials, (also known as A-π-A quasi-macromolecule (QM) acceptors) have attracted considerable attention in organic solar cells (OSCs) due to their well-defined structures, batch reproducibility, improved morphology, enhanced stability etc. Altering the π bridge unit is a simple yet effective way to modulate molecular configuration and packing motifs, and thus affecting the efficiency of the resulting OSCs. Herein, we synthesized three A-π-A QM acceptors, QM-1T, QM-2T and QM-3T, with different conjugation length of π bridge units (thiophene, bithiophene and terthiophene) and studied exquisitely controlling the molecular size to influence the active-layer morphology and device performance. The theoretical calculations and experimental characterization results show that QM-2T exhibits an increased absorption, upshifted LUMO level and more ordered stacking pattern thanks to the relatively suitable π bridge length. The well-controlled morphology in the blend of PM6:QM-2T also results in the much-improved and balanced electron and hole mobility. Accordingly, QM-2T-based OSC achieves a high open circuit voltage of 0.94 V without sacrificing short circuit current density, resulting for a higher device efficiency of 17.86% than QM-1T and QM-3T. These results highlight the significance of molecular geometric design by featuring conjugated π bridge lengths to achieve high-performance OSCs.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431347","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}
Yan Wan, Chen Fang, Xu Yang, Jinli Liu, Yangming Lin
Heterogeneous catalysis has been inseparable from the fields of energy-related conversion and organic synthesis, etc. By virtue of the merits of low cost, earth-abundance, and low toxicity, metal-free catalysts, as alternative to metal-based catalyst, have been paid considerable attention. Amongst them, borocarbonitride materials emerges as an important class of layered metal-free functional material and possess a variety of stoichiometry and crystal structure, exhibiting some unique properties, such as tunable bandgap, good thermal conductivity, large surface area etc. and thereby being used as catalyst in various conversions. In the present review, we begin with an introduction of the structure and theoretical simulation of borocarbonitride materials, followed by a summary of the synthesis methods reported in the last five years. Then, in terms of the specific reactions, the recent representative research progress of borocarbonitride in the fields of thermocatalysis, electrocatalysis, and photocatalysis are discussed in detail. Finally, the challenges confronting in current research are pointed out and the future perspective are offered.
{"title":"Borocarbonitride materials as metal-free catalysts for advanced catalysis","authors":"Yan Wan, Chen Fang, Xu Yang, Jinli Liu, Yangming Lin","doi":"10.1039/d4ta04797d","DOIUrl":"https://doi.org/10.1039/d4ta04797d","url":null,"abstract":"Heterogeneous catalysis has been inseparable from the fields of energy-related conversion and organic synthesis, etc. By virtue of the merits of low cost, earth-abundance, and low toxicity, metal-free catalysts, as alternative to metal-based catalyst, have been paid considerable attention. Amongst them, borocarbonitride materials emerges as an important class of layered metal-free functional material and possess a variety of stoichiometry and crystal structure, exhibiting some unique properties, such as tunable bandgap, good thermal conductivity, large surface area etc. and thereby being used as catalyst in various conversions. In the present review, we begin with an introduction of the structure and theoretical simulation of borocarbonitride materials, followed by a summary of the synthesis methods reported in the last five years. Then, in terms of the specific reactions, the recent representative research progress of borocarbonitride in the fields of thermocatalysis, electrocatalysis, and photocatalysis are discussed in detail. Finally, the challenges confronting in current research are pointed out and the future perspective are offered.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431346","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}
Asymmetric substitution on donors has been shown to be an effective approach to optimize the morphology and the photovoltaic performance of all-small-molecule organic solar cells (ASM-OSCs), but this strategy is rarely applied in liquid crystalline small molecule donors (SMDs). Herein, one of two rhodanine (R) end groups on the well-known liquid crystalline molecule BTR-Cl is replaced by 2-ethylhexyl cyanoacetate (CA), yielding three new asymmetric SMDs, BT-CAR2, BT-CAR4, and BT-CAR6, whose lengths of alkyl chains on the rhodanine groups are 2, 4, and 6 carbon atoms, respectively. The asymmetric structure enhances intermolecular interactions and three SMDs all exhibit highly ordered edge-on orientations in the solid states. Notably, the BT-CAR4:Y6 film achieves a finely tuned morphology due to the optimal miscibility between BT-CAR4 and Y6. Consequently, all three ASM-OSCs exhibit efficiencies of around 15%, significantly surpassing the previously reported efficiency of the BTR-Cl based counterpart (13.6%). Specifically, the BT-CAR4:Y6 device achieves the highest efficiency of 15.52%. This work presents a promising avenue for designing efficient SMDs for ASM-OSCs.
{"title":"Asymmetric liquid crystalline donors with two different end groups enable efficient all-small-molecule organic solar cells","authors":"Chenhe Wang, Tianyi Chen, Shuixing Li, Yecheng Shen, Jinyang Yu, Adiljan Wupur, Yongmin Luo, Mengting Wang, Xiukun Ye, Jiaying Wu, Minmin Shi, Hongzheng Chen","doi":"10.1039/d4ta06126h","DOIUrl":"https://doi.org/10.1039/d4ta06126h","url":null,"abstract":"Asymmetric substitution on donors has been shown to be an effective approach to optimize the morphology and the photovoltaic performance of all-small-molecule organic solar cells (ASM-OSCs), but this strategy is rarely applied in liquid crystalline small molecule donors (SMDs). Herein, one of two rhodanine (R) end groups on the well-known liquid crystalline molecule BTR-Cl is replaced by 2-ethylhexyl cyanoacetate (CA), yielding three new asymmetric SMDs, BT-CAR2, BT-CAR4, and BT-CAR6, whose lengths of alkyl chains on the rhodanine groups are 2, 4, and 6 carbon atoms, respectively. The asymmetric structure enhances intermolecular interactions and three SMDs all exhibit highly ordered edge-on orientations in the solid states. Notably, the BT-CAR4:Y6 film achieves a finely tuned morphology due to the optimal miscibility between BT-CAR4 and Y6. Consequently, all three ASM-OSCs exhibit efficiencies of around 15%, significantly surpassing the previously reported efficiency of the BTR-Cl based counterpart (13.6%). Specifically, the BT-CAR4:Y6 device achieves the highest efficiency of 15.52%. This work presents a promising avenue for designing efficient SMDs for ASM-OSCs.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431345","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}
Mingzhe Sun, Tianqi Wang, Calvin Ku, Aamir Hanif, Tian Tian, Bernt Johannessen, Qinfen Gu, Ziyi Li, Patrick H-L Sit, Jin Shang
Atmospheric NO2 pollution poses significant risks to human health and the environment even at low concentrations, necessitating the development of efficient technologies for its removal under ambient conditions. This study developed copper (Cu)-modified SSZ-13 zeolites (referred to as Cun+SSZ-13 where n represents the valence state of Cu) for NO2 removal by adsorption. Cun+SSZ-13 zeolites containing Cu species with different valence states and proportions were prepared by reducing Cu2+-exchanged SSZ-13 zeolite (Cu2+SSZ-13) using H2 at different temperatures. The Cun+SSZ-13 reduced at 190 oC showed the highest NO2 removal capacity (1.79 mmol/g), outperforming prinstine SSZ-13 and Cu2+SSZ-13 by 52.3% and 19.4%, respectively. The improvement was due to the increased amount of adsorption sites (Cu+ and H+) and the stronger affinity of Cu+ than Cu2+ towards NO2, as confirmed by density functional theory (DFT) calculations. The generation of Cu0 nanoparticles and moisture in zeolites during reduction were undesirable for NO2 adsorption. However, this could be eliminated by lowering the reduction temperature and applying a thermal activation, respectively. This work provides systematical methods for designing zeolite adsorbents for ambient NO2 removal and offers insights into the burgeoning filed of air pollution control.
{"title":"Regulating NO2 adsorption at ambient temperature by manipulating copper species as binding sites in copper-modified SSZ-13 zeolites","authors":"Mingzhe Sun, Tianqi Wang, Calvin Ku, Aamir Hanif, Tian Tian, Bernt Johannessen, Qinfen Gu, Ziyi Li, Patrick H-L Sit, Jin Shang","doi":"10.1039/d4ta04399e","DOIUrl":"https://doi.org/10.1039/d4ta04399e","url":null,"abstract":"Atmospheric NO2 pollution poses significant risks to human health and the environment even at low concentrations, necessitating the development of efficient technologies for its removal under ambient conditions. This study developed copper (Cu)-modified SSZ-13 zeolites (referred to as Cun+SSZ-13 where n represents the valence state of Cu) for NO2 removal by adsorption. Cun+SSZ-13 zeolites containing Cu species with different valence states and proportions were prepared by reducing Cu2+-exchanged SSZ-13 zeolite (Cu2+SSZ-13) using H2 at different temperatures. The Cun+SSZ-13 reduced at 190 oC showed the highest NO2 removal capacity (1.79 mmol/g), outperforming prinstine SSZ-13 and Cu2+SSZ-13 by 52.3% and 19.4%, respectively. The improvement was due to the increased amount of adsorption sites (Cu+ and H+) and the stronger affinity of Cu+ than Cu2+ towards NO2, as confirmed by density functional theory (DFT) calculations. The generation of Cu0 nanoparticles and moisture in zeolites during reduction were undesirable for NO2 adsorption. However, this could be eliminated by lowering the reduction temperature and applying a thermal activation, respectively. This work provides systematical methods for designing zeolite adsorbents for ambient NO2 removal and offers insights into the burgeoning filed of air pollution control.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431342","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}
Yahui Tian, Wenfang Zhai, Jie Su, Yuxin Zhao, Zhengfei Dai, Wei Gan, Hui Li
The selective detection of toxic gases is crucial for human health and air-quality monitoring, necessitating specialized customizations in the structure of sensing materials. In this study, we have profiled a black phosphorene (BP) hosted NiO nanosheet heterostructure for the sensitive and selective detection of trace H2S gas. Both the theoretical and experimental investigations have indicated the electron transfer from the BP to NiO at the p-p interface, resulting in the electron-rich state of NiO and enhanced surface Lewis basicity. Such a Lewis basic surface would intrinsically empower the acidic H2S adsorption towards the boosted H2S detection. Resultantly, the optimized NiO/BP heterostructure showcases the improved H2S sensing response with 1.9 and 3.5 times higher than those of NiO and BP at 150 °C to 5 ppm H2S. It also illustrates the stable sensing with fast kinetics, low detectable limit (50 ppb), enhanced humid-resistivity, and H2S selectivity. Computational calculations suggest that the NiO/BP structure can realize the chemisorption manner with a negative free energy (-0.82 eV) toward sensitive/selective H2S sensing. This research puts forward the surface acidity/basicity as the criterion in rationalizing the efficient H2S sensor through interface modification.
{"title":"Enhancing the Surface Lewis Basicity of Phosphorene-Hosted NiO Nanosheets for Sensitive and Selective H2S Gas Sensing","authors":"Yahui Tian, Wenfang Zhai, Jie Su, Yuxin Zhao, Zhengfei Dai, Wei Gan, Hui Li","doi":"10.1039/d4ta05682e","DOIUrl":"https://doi.org/10.1039/d4ta05682e","url":null,"abstract":"The selective detection of toxic gases is crucial for human health and air-quality monitoring, necessitating specialized customizations in the structure of sensing materials. In this study, we have profiled a black phosphorene (BP) hosted NiO nanosheet heterostructure for the sensitive and selective detection of trace H2S gas. Both the theoretical and experimental investigations have indicated the electron transfer from the BP to NiO at the p-p interface, resulting in the electron-rich state of NiO and enhanced surface Lewis basicity. Such a Lewis basic surface would intrinsically empower the acidic H2S adsorption towards the boosted H2S detection. Resultantly, the optimized NiO/BP heterostructure showcases the improved H2S sensing response with 1.9 and 3.5 times higher than those of NiO and BP at 150 °C to 5 ppm H2S. It also illustrates the stable sensing with fast kinetics, low detectable limit (50 ppb), enhanced humid-resistivity, and H2S selectivity. Computational calculations suggest that the NiO/BP structure can realize the chemisorption manner with a negative free energy (-0.82 eV) toward sensitive/selective H2S sensing. This research puts forward the surface acidity/basicity as the criterion in rationalizing the efficient H2S sensor through interface modification.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431165","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}
Hanie Sharifpour, Farzaneh Hekmat, Saeed Shahrokhian, Likun Pan
Two-third coverage of the Earth’s surface, saltwater softening sounds like the most feasible approach to bridging the gap between drinking water generation and its growing demand. Today numerous capacitive devices have been developed for emerging either water softening or charge storage from resource recovery, their dual potent functionality has been rarely investigated. The reinforced selective sodium-removal and charge-storage capacities using a combination between sodium capturing in sorption step and sodium releasing from regeneration step through a CDI process. Leveraging unique and reversible Na+-removal character, sodium superionic conductors (NASICON)-particularly those altered using carbons, emerge as prospective candidates for hybrid capacitive deionization (HCDI). Despite the great desalination ability of HCDIs, the unbalanced ion-capturing and rising possibility of co-ion expulsion has led up to a real bottleneck can significantly tackle with placing an ion exchange membrane (IEM) between the electrolyte and the electrode. Herein, the state-of-the-art Na+ selective technology has been engineered using well-matched carbon-coated NaTi2(PO4)3 (NTP−C) and N-rich carbon nests (NCNs) as negative and positive electrodes, respectively. The performance of the fabricated HCDI benefit from a commendable salt adsorption capacity (SAC) of 96.8 mg g−1, salt adsorption rate (SAR) of 2.42 mg g−1 min−1, specific energy consumption (Es) of 18.5 j mg−1NaCl within sorption step, alongside perfect energy storage capacity (Q) of 46.52 C g−1 in very low concentration of 500 ppm of NaCl in regeneration step. The NTP−C//NCN HCDI systems rendered remarkable cycle stability with almost over 92.3 and 91.3% retention in salt adsorption and charge storage capacities, respectively, after 30 continuous cycles. The Na+ selective remove-capability of the fabricated HCDIs was explored by comparing their Na+ removal capacity in the absence and presence of Mg2+, Ca2+ and K+ ions (S Na+/X > 2.5) which rendered a superior sodium removal efficiency (SRE%) of almost over 50% from both pure and contaminated mixtures. All in all, high-yield energy-efficient HCDI device with remarkable Na+ selectivity was developed, which sound promising for selective ion removal even in the coexistence of background ions. As a direct consequence of high charge storage capacity, the fabricated HCDI deserve credit for energy applications, so inaugurations a pioneer horizon towards the commercialization of HCDI technologies.
{"title":"Towards Advanced Electrochemical Horizon: Ion Selectivity and Energy Harnessing Through Hybrid Capacitive Deionization with Carbon-Coated NaTi2(PO4)3 and N-rich Carbon Nests","authors":"Hanie Sharifpour, Farzaneh Hekmat, Saeed Shahrokhian, Likun Pan","doi":"10.1039/d4ta04413d","DOIUrl":"https://doi.org/10.1039/d4ta04413d","url":null,"abstract":"Two-third coverage of the Earth’s surface, saltwater softening sounds like the most feasible approach to bridging the gap between drinking water generation and its growing demand. Today numerous capacitive devices have been developed for emerging either water softening or charge storage from resource recovery, their dual potent functionality has been rarely investigated. The reinforced selective sodium-removal and charge-storage capacities using a combination between sodium capturing in sorption step and sodium releasing from regeneration step through a CDI process. Leveraging unique and reversible Na+-removal character, sodium superionic conductors (NASICON)-particularly those altered using carbons, emerge as prospective candidates for hybrid capacitive deionization (HCDI). Despite the great desalination ability of HCDIs, the unbalanced ion-capturing and rising possibility of co-ion expulsion has led up to a real bottleneck can significantly tackle with placing an ion exchange membrane (IEM) between the electrolyte and the electrode. Herein, the state-of-the-art Na+ selective technology has been engineered using well-matched carbon-coated NaTi2(PO4)3 (NTP−C) and N-rich carbon nests (NCNs) as negative and positive electrodes, respectively. The performance of the fabricated HCDI benefit from a commendable salt adsorption capacity (SAC) of 96.8 mg g−1, salt adsorption rate (SAR) of 2.42 mg g−1 min−1, specific energy consumption (Es) of 18.5 j mg−1NaCl within sorption step, alongside perfect energy storage capacity (Q) of 46.52 C g−1 in very low concentration of 500 ppm of NaCl in regeneration step. The NTP−C//NCN HCDI systems rendered remarkable cycle stability with almost over 92.3 and 91.3% retention in salt adsorption and charge storage capacities, respectively, after 30 continuous cycles. The Na+ selective remove-capability of the fabricated HCDIs was explored by comparing their Na+ removal capacity in the absence and presence of Mg2+, Ca2+ and K+ ions (S Na+/X > 2.5) which rendered a superior sodium removal efficiency (SRE%) of almost over 50% from both pure and contaminated mixtures. All in all, high-yield energy-efficient HCDI device with remarkable Na+ selectivity was developed, which sound promising for selective ion removal even in the coexistence of background ions. As a direct consequence of high charge storage capacity, the fabricated HCDI deserve credit for energy applications, so inaugurations a pioneer horizon towards the commercialization of HCDI technologies.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431402","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}
Lead-free dielectric ceramics are one of the most essential candidates for reforming pulsed power capacitors, nevertheless the formidable hurdles posed by the high hysteresis and low energy storage properties. Dielectric ceramic capacitors with ultra-high energy storage performance usually need to be realized under the condition of high electric field. Its application in miniaturized integrated electronic devices is severely limited. In this work, the A-site deficiency is designed in Na0.97Bi0.01TaO3-modified Bi0.48Na0.48Ba0.04TiO3 lead-free relaxor ferroelectric ceramics to increase oxygen vacancy content, achieve local disorder and construct local multi-phase coexistence. Which causes low hysteresis with excellent high energy density at low electric fields (LEFs). The conclusions indicate that introduction of A-site deficiency would improve the concentration of oxygen vacancy while reconstructing the local structure disorder. Benefiting from the synergistic effect of both, A high energy recoverable density of ~7.98 J cm−3 and an efficiency of ~83.7% can be measured in 0.84Bi0.48Na0.48Ba0.04TiO3-0.16Na0.97Bi0.01TaO3 modified ceramics under 330 kV cm−1. Furthermore, the modified ceramics have acceptable frequency stability (0.5–130 Hz) and temperature stability (RT–180 °C) with exactly discharge density. This finding develops an innovative strategy for fabricate energy-storage ceramics under low electric field conditions.
{"title":"Achieved Excellent Low-field Energy Storage Properties and High Density in Bi0.48Na0.48Ba0.04TiO3-based Oxide Ceramics via The Interposing of (Na0.97Bi0.01)+/Ta5+ at A/B Sites","authors":"Jiwei Du, Tianhui Shi, Qin Feng, Ronghao Jia, Jianan Hu, Changlai Yuan, Xinpeng Wang, Xiyong Chen, Nengneng Luo, Jiwei Zhai","doi":"10.1039/d4ta06319h","DOIUrl":"https://doi.org/10.1039/d4ta06319h","url":null,"abstract":"Lead-free dielectric ceramics are one of the most essential candidates for reforming pulsed power capacitors, nevertheless the formidable hurdles posed by the high hysteresis and low energy storage properties. Dielectric ceramic capacitors with ultra-high energy storage performance usually need to be realized under the condition of high electric field. Its application in miniaturized integrated electronic devices is severely limited. In this work, the A-site deficiency is designed in Na0.97Bi0.01TaO3-modified Bi0.48Na0.48Ba0.04TiO3 lead-free relaxor ferroelectric ceramics to increase oxygen vacancy content, achieve local disorder and construct local multi-phase coexistence. Which causes low hysteresis with excellent high energy density at low electric fields (LEFs). The conclusions indicate that introduction of A-site deficiency would improve the concentration of oxygen vacancy while reconstructing the local structure disorder. Benefiting from the synergistic effect of both, A high energy recoverable density of ~7.98 J cm−3 and an efficiency of ~83.7% can be measured in 0.84Bi0.48Na0.48Ba0.04TiO3-0.16Na0.97Bi0.01TaO3 modified ceramics under 330 kV cm−1. Furthermore, the modified ceramics have acceptable frequency stability (0.5–130 Hz) and temperature stability (RT–180 °C) with exactly discharge density. This finding develops an innovative strategy for fabricate energy-storage ceramics under low electric field conditions.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431406","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}
The hydrogen evolution reaction (HER) on platinum electrocatalysts involves the generation of hydrogen atoms and the formation of hydrogen molecules. It is commonly believed that the sites on the surfaces of the terrace (111, 110, and 100) domains are responsible for the formation of hydrogen molecules. However, the electrochemistry of the hydrogen atom generation is not well understood. We created edge-rich platinum electrocatalysts by using nano-fabrics comprising entire single-walled carbon nanotubes (SWCNTs) as templates and supports. We then conducted the HER on the edge-rich platinum/SWCNT hybridized electrocatalysts and gained new insights into the electrochemical properties and functions of the edge sites. We propose that the edge sites are oxidized and serve two important functions: they act as atomic barriers, allowing electrons to accumulate within the terrace (111, 110, and 100) domains, and they transfer the electrons to the hydronium ions in the electrical double layer through discharge. Enhancing the discharge capability of the electrocatalysts is an efficient way to reduce the amount of platinum required, and this can be applied to various precious metal-based electrocatalysts to enhance their electrocatalytic activities and durability.
铂电催化剂上的氢进化反应（HER）涉及氢原子的生成和氢分子的形成。人们普遍认为，台阶（111、110 和 100）表面的位点是形成氢分子的原因。然而，人们对氢原子生成的电化学原理并不十分了解。我们利用由整根单壁碳纳米管（SWCNT）组成的纳米织物作为模板和支撑，制造出了富集边缘的铂电催化剂。然后，我们对富集边缘铂/SWCNT 杂化电催化剂进行了 HER 研究，对边缘位点的电化学性质和功能有了新的认识。我们认为，边缘位点是氧化的，具有两个重要功能：作为原子屏障，允许电子在台阶（111、110 和 100）畴内聚集；通过放电将电子转移到电双层中的氢离子。增强电催化剂的放电能力是减少铂金用量的有效方法，可应用于各种贵金属电催化剂，以提高其电催化活性和耐久性。
{"title":"Edge sites on platinum electrocatalysts are responsible for discharge in the hydrogen evolution reaction","authors":"Vipin Adavan Kiliyankil, Wei Mao, Yurie Takahashi, Wei Gong, Shigeru Kabayama, Yuki Hamasaki, Katsuyuki Fukutani, Hiroyuki Matsuzaki, Ichiro Sakata, Kenji Takeuchi, Morinobu Endo, Bunshi Fugetsu","doi":"10.1039/d4ta04887c","DOIUrl":"https://doi.org/10.1039/d4ta04887c","url":null,"abstract":"The hydrogen evolution reaction (HER) on platinum electrocatalysts involves the generation of hydrogen atoms and the formation of hydrogen molecules. It is commonly believed that the sites on the surfaces of the terrace (111, 110, and 100) domains are responsible for the formation of hydrogen molecules. However, the electrochemistry of the hydrogen atom generation is not well understood. We created edge-rich platinum electrocatalysts by using nano-fabrics comprising entire single-walled carbon nanotubes (SWCNTs) as templates and supports. We then conducted the HER on the edge-rich platinum/SWCNT hybridized electrocatalysts and gained new insights into the electrochemical properties and functions of the edge sites. We propose that the edge sites are oxidized and serve two important functions: they act as atomic barriers, allowing electrons to accumulate within the terrace (111, 110, and 100) domains, and they transfer the electrons to the hydronium ions in the electrical double layer through discharge. Enhancing the discharge capability of the electrocatalysts is an efficient way to reduce the amount of platinum required, and this can be applied to various precious metal-based electrocatalysts to enhance their electrocatalytic activities and durability.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431167","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}
Metal sulfides are prominent candidates for sodium-ion batteries (SIBs) anodes owing to their high theoretical capacities and superior conductivities, but their performance is hindered by volume expansion during cycling. This study introduces an approach for mitigating these issues by incorporating high-entropy structures into sulfides. We synthesized a high-entropy sulfide (HES) (FeCoNiCuZn)In2S4 (MS5) and medium- and low-entropy sulfides for comparison. Physical and chemical characterization confirmed the successful formation of the HES, the uniform distribution of elements and the presence of sulfur vacancies. We show that high-entropy doping shows alleviate volume expansion during cycling and enhance sodium storage capacity, thereby improving electrochemical performance. After 800 cycles at a current density of 1 A g-1, MS5 exhibits a reversible capacity of 412.7 mAh g-1. When the current density is increased to 5 A g-1, it can still stably cycle for 800 cycles with a capacity retention rate of up to 88%. Density functional theory calculations supported the experimental findings, indicating that the introduction of high-entropy structures enhances the structural stability and Na+ migration, and increases the number of reactive sites. This study highlights the potential of HES materials for use in the anode of next-generation SIBs, offering insights into their design and application in improved energy-storage solutions.
金属硫化物因其理论容量高、导电性能优异而成为钠离子电池（SIBs）阳极的主要候选材料，但在循环过程中其性能会受到体积膨胀的影响。本研究介绍了一种通过在硫化物中加入高熵结构来缓解这些问题的方法。我们合成了高熵硫化物 (HES) (FeCoNiCuZn)In2S4 (MS5)，并合成了中熵和低熵硫化物进行比较。物理和化学表征证实了高熵硫化物的成功形成、元素的均匀分布以及硫空位的存在。我们的研究表明，高熵掺杂可以缓解循环过程中的体积膨胀，提高钠的存储容量，从而改善电化学性能。在电流密度为 1 A g-1 的条件下循环 800 次后，MS5 显示出 412.7 mAh g-1 的可逆容量。当电流密度增加到 5 A g-1 时，它仍能稳定地循环 800 次，容量保持率高达 88%。密度泛函理论计算支持了实验结果，表明高熵结构的引入增强了结构稳定性和 Na+ 迁移，并增加了反应位点的数量。这项研究凸显了 HES 材料用于下一代 SIB 阳极的潜力，为它们在改进型储能解决方案中的设计和应用提供了启示。
{"title":"Sodium Storage Performance of a High Entropy Sulfide Anode with Reduced Volume Expansion","authors":"Jianping Ma, Jinyi Guo, Weizheng Li, Xiaohan Yang, Chengde Huang","doi":"10.1039/d4ta05122j","DOIUrl":"https://doi.org/10.1039/d4ta05122j","url":null,"abstract":"Metal sulfides are prominent candidates for sodium-ion batteries (SIBs) anodes owing to their high theoretical capacities and superior conductivities, but their performance is hindered by volume expansion during cycling. This study introduces an approach for mitigating these issues by incorporating high-entropy structures into sulfides. We synthesized a high-entropy sulfide (HES) (FeCoNiCuZn)In2S4 (MS5) and medium- and low-entropy sulfides for comparison. Physical and chemical characterization confirmed the successful formation of the HES, the uniform distribution of elements and the presence of sulfur vacancies. We show that high-entropy doping shows alleviate volume expansion during cycling and enhance sodium storage capacity, thereby improving electrochemical performance. After 800 cycles at a current density of 1 A g-1, MS5 exhibits a reversible capacity of 412.7 mAh g-1. When the current density is increased to 5 A g-1, it can still stably cycle for 800 cycles with a capacity retention rate of up to 88%. Density functional theory calculations supported the experimental findings, indicating that the introduction of high-entropy structures enhances the structural stability and Na+ migration, and increases the number of reactive sites. This study highlights the potential of HES materials for use in the anode of next-generation SIBs, offering insights into their design and application in improved energy-storage solutions.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431176","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}
Sodium-ion batteries are a promising area of research, and phosphate-based sodium superionic conductor (NASICON) materials have received significant attention from researchers due to their high structural stability and ionic conductivity. First principles calculations have been employed to facilitate the research process. This paper introduces the application of first principles calculations in the study of battery materials. It reviews the research progress of the application of first principles calculations in phosphate-based NASICON structured cathode, anode and electrolyte materials, which mainly include the intrinsic properties of the materials and the study of ionic doping modification of some of the materials. It is demonstrated that NASICON materials exhibit excellent structural stability, an appropriate working voltage (approximately 2–4.2 V for cathode materials and below 2 V for anode materials) and an exceptional sodium ion transport performance (Na+ migration barrier less than 1 eV), which collectively render them highly promising for application. However, the poor electronic conductivity (mostly semiconductor materials, with a band gap of 2–3 eV or so) limits the performance of the material. Ion doping can improve the electronic conductivity of the material to a certain extent, but the NASICON battery materials still cannot be compared with the current commercial lithium-ion battery materials. Consequently, multiple ion doping and conductive material modification will be some of the future research directions. As computers and computing software progress, first principles calculations could eventually become the standard approach for studying battery materials. This strategy might make it more straightforward to select the best battery materials and modification methods while including experimental testing to enhance the phosphate-based NASICON materials' overall performance and develop new battery materials.
{"title":"Advances in the application of first principles calculations to phosphate-based NASICON battery materials","authors":"Zhongyi Cui, Shilong Sun, Gexuan Ning, Lisi Liang, Zeming Wang, Jiangyu Qiao, Lixing Zhang, Jin Chen, Zhuyue Zhang","doi":"10.1039/d4ta04943h","DOIUrl":"https://doi.org/10.1039/d4ta04943h","url":null,"abstract":"Sodium-ion batteries are a promising area of research, and phosphate-based sodium superionic conductor (NASICON) materials have received significant attention from researchers due to their high structural stability and ionic conductivity. First principles calculations have been employed to facilitate the research process. This paper introduces the application of first principles calculations in the study of battery materials. It reviews the research progress of the application of first principles calculations in phosphate-based NASICON structured cathode, anode and electrolyte materials, which mainly include the intrinsic properties of the materials and the study of ionic doping modification of some of the materials. It is demonstrated that NASICON materials exhibit excellent structural stability, an appropriate working voltage (approximately 2–4.2 V for cathode materials and below 2 V for anode materials) and an exceptional sodium ion transport performance (Na<small><sup>+</sup></small> migration barrier less than 1 eV), which collectively render them highly promising for application. However, the poor electronic conductivity (mostly semiconductor materials, with a band gap of 2–3 eV or so) limits the performance of the material. Ion doping can improve the electronic conductivity of the material to a certain extent, but the NASICON battery materials still cannot be compared with the current commercial lithium-ion battery materials. Consequently, multiple ion doping and conductive material modification will be some of the future research directions. As computers and computing software progress, first principles calculations could eventually become the standard approach for studying battery materials. This strategy might make it more straightforward to select the best battery materials and modification methods while including experimental testing to enhance the phosphate-based NASICON materials' overall performance and develop new battery materials.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431171","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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