Pub Date : 2024-10-18DOI: 10.1038/s41427-024-00555-7
Junghwan Sung, Junyoung Heo, Dong-Hee Kim, Hawon Gu, Yung-Soo Jo, Heetaek Park, Jun-Ho Park, Jeong-Hee Choi, Yoon-Cheol Ha, Doohun Kim, Jun-Woo Park
All-solid-state batteries (ASSBs) with adequately selected cathode materials exhibit a higher energy density and better safety than conventional lithium-ion batteries (LIBs). Ni-rich layered cathodes are benchmark materials for traditional LIBs owing to their high energy density. Recent studies have highlighted the advantages of using crack-free, single-crystalline cathode materials in ASSBs. In this study, a scalable infiltration sheet-type process was used to fabricate composite electrodes with different cathode-material morphologies for ASSBs. Typically, crack-free single-crystalline materials exhibit better retention performance and lower rate capability (i.e., slower kinetics in charge‒discharge processes) than polycrystalline cathode materials. Li6PS5Cl-infiltrated polycrystalline electrodes showed excellent retention performance and rate capability. Galvanostatic intermittent titration technique analysis and transmission electron microscopy of the single-crystalline electrode confirmed severe polarization and the presence of a rock-salt-structure layer in the cathode particles; these results indicated side reactions within the layered structure of the material. In contrast, composite electrodes consisting of polycrystalline cathode materials infiltrated with the solid electrolyte Li6PS5Cl showed excellent electrochemical performance owing to intimate electrode–electrolyte interfacial contact. The result from this study confirmed the critical influence of interface engineering and material morphology on the overall performance and stability of ASSBs and could facilitate the development of high-performance ASSBs in the future. This study introduces a technique for utilizing conventional lithium-ion battery electrodes in all-solid-state batteries. By infiltrating a solid electrolyte solution into the porous electrode, the effects based on the morphology of the active material were investigated. In poly-crystalline materials, high coverage and the formation of a thin side reaction layer were observed. Consequently, the infiltration process also confirmed the superior performance of poly-crystalline materials.
{"title":"Infiltration-driven performance enhancement of poly-crystalline cathodes in all-solid-state batteries","authors":"Junghwan Sung, Junyoung Heo, Dong-Hee Kim, Hawon Gu, Yung-Soo Jo, Heetaek Park, Jun-Ho Park, Jeong-Hee Choi, Yoon-Cheol Ha, Doohun Kim, Jun-Woo Park","doi":"10.1038/s41427-024-00555-7","DOIUrl":"10.1038/s41427-024-00555-7","url":null,"abstract":"All-solid-state batteries (ASSBs) with adequately selected cathode materials exhibit a higher energy density and better safety than conventional lithium-ion batteries (LIBs). Ni-rich layered cathodes are benchmark materials for traditional LIBs owing to their high energy density. Recent studies have highlighted the advantages of using crack-free, single-crystalline cathode materials in ASSBs. In this study, a scalable infiltration sheet-type process was used to fabricate composite electrodes with different cathode-material morphologies for ASSBs. Typically, crack-free single-crystalline materials exhibit better retention performance and lower rate capability (i.e., slower kinetics in charge‒discharge processes) than polycrystalline cathode materials. Li6PS5Cl-infiltrated polycrystalline electrodes showed excellent retention performance and rate capability. Galvanostatic intermittent titration technique analysis and transmission electron microscopy of the single-crystalline electrode confirmed severe polarization and the presence of a rock-salt-structure layer in the cathode particles; these results indicated side reactions within the layered structure of the material. In contrast, composite electrodes consisting of polycrystalline cathode materials infiltrated with the solid electrolyte Li6PS5Cl showed excellent electrochemical performance owing to intimate electrode–electrolyte interfacial contact. The result from this study confirmed the critical influence of interface engineering and material morphology on the overall performance and stability of ASSBs and could facilitate the development of high-performance ASSBs in the future. This study introduces a technique for utilizing conventional lithium-ion battery electrodes in all-solid-state batteries. By infiltrating a solid electrolyte solution into the porous electrode, the effects based on the morphology of the active material were investigated. In poly-crystalline materials, high coverage and the formation of a thin side reaction layer were observed. Consequently, the infiltration process also confirmed the superior performance of poly-crystalline materials.","PeriodicalId":19382,"journal":{"name":"Npg Asia Materials","volume":"16 1","pages":"1-9"},"PeriodicalIF":8.6,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41427-024-00555-7.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143187383","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nitrogen-containing compounds such as imides and amides have been reported as efficient materials that promote ammonia decomposition over nonnoble metal catalysts. However, these compounds decompose in an air atmosphere and become inactive, which leads to difficulty in handling. Here, we focused on perovskite oxynitrides as air-stable and efficient supports for ammonia decomposition catalysts. Ni-loaded oxynitrides exhibited 2.5–18 times greater catalytic activity than did the corresponding oxide-supported Ni catalysts, even without noticeable differences in the Ni particle size and surface area of the supports. The catalytic performance of the Ni-loaded oxynitrides is well correlated with the nitrogen desorption temperature during N2 temperature-programmed desorption, which suggests that the lattice nitrogen in the oxynitride support rather than the Ni surface is the active site for ammonia decomposition. Furthermore, NH3 temperature-programmed surface reactions and density functional theory (DFT) calculations revealed that NH3 molecules are preferentially adsorbed on the nitrogen vacancy sites on the support surface rather than on the Ni surface. Thus, the ammonia decomposition reaction is facilitated by a vacancy-mediated reaction mechanism. Oxynitride-supported Ni catalysts exhibit much higher activity than oxide-supported Ni catalysts for ammonia decomposition reaction. Ammonia is activated at nitrogen vacancy sites on the surface of oxynitride in close vicinity to the supported Ni nanoparticles rather than on the Ni surface, and therefore the catalytic performance is dominated by ease of nitrogen vacancy formation on the catalyst surface.
{"title":"Effects of nitrogen vacancy sites of oxynitride support on the catalytic activity for ammonia decomposition","authors":"Kazuki Miyashita, Kiya Ogasawara, Masayoshi Miyazaki, Hitoshi Abe, Yasuhiro Niwa, Hideki Kato, Hideo Hosono, Masaaki Kitano","doi":"10.1038/s41427-024-00572-6","DOIUrl":"10.1038/s41427-024-00572-6","url":null,"abstract":"Nitrogen-containing compounds such as imides and amides have been reported as efficient materials that promote ammonia decomposition over nonnoble metal catalysts. However, these compounds decompose in an air atmosphere and become inactive, which leads to difficulty in handling. Here, we focused on perovskite oxynitrides as air-stable and efficient supports for ammonia decomposition catalysts. Ni-loaded oxynitrides exhibited 2.5–18 times greater catalytic activity than did the corresponding oxide-supported Ni catalysts, even without noticeable differences in the Ni particle size and surface area of the supports. The catalytic performance of the Ni-loaded oxynitrides is well correlated with the nitrogen desorption temperature during N2 temperature-programmed desorption, which suggests that the lattice nitrogen in the oxynitride support rather than the Ni surface is the active site for ammonia decomposition. Furthermore, NH3 temperature-programmed surface reactions and density functional theory (DFT) calculations revealed that NH3 molecules are preferentially adsorbed on the nitrogen vacancy sites on the support surface rather than on the Ni surface. Thus, the ammonia decomposition reaction is facilitated by a vacancy-mediated reaction mechanism. Oxynitride-supported Ni catalysts exhibit much higher activity than oxide-supported Ni catalysts for ammonia decomposition reaction. Ammonia is activated at nitrogen vacancy sites on the surface of oxynitride in close vicinity to the supported Ni nanoparticles rather than on the Ni surface, and therefore the catalytic performance is dominated by ease of nitrogen vacancy formation on the catalyst surface.","PeriodicalId":19382,"journal":{"name":"Npg Asia Materials","volume":"16 1","pages":"1-9"},"PeriodicalIF":8.6,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41427-024-00572-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143187395","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study aimed to investigate the anticancer efficacy and underlying mechanism of novel platinum nanoclusters (Pt NCs) in osteosarcoma cell lines exhibiting distinct P53 expression profiles, namely MG-63 (P53−) and U2-OS (P53+). The findings revealed that Pt NCs exerted an inhibitory effect on proliferation, migration, and colony formation while promoting apoptosis in both MG-63 (P53−) and U2-OS (P53+) cells. The inhibitory effect on the malignant characteristics of MG-63 (P53−) cells was more obvious, indicating that the potential anticancer effect of Pt NCs was not dependent on P53. Animal experiments have substantiated the in vivo anticancer properties of Pt NCs, while also revealing their lower toxicity on cells and tissues. Pt NCs possess the ability to impede cell proliferation by inducing DNA damage and arresting the cell cycle in the G1 phase and possess the ability to promote BAX/Bcl-2/Caspase-3/mitochondrial apoptosis. Pt NCs may promote mitochondrial apoptosis by promoting damaging autophagy, thereby promoting cellular demise. This study has confirmed the P53-independent anticancer impact of Pt NCs on osteosarcoma in vitro and in vivo. Pt NCs may play a therapeutic role in more sensitive MG-63 (P53−) cells by promoting DNA damage to arrest the cell cycle, stimulating BAX/Bcl-2/Caspase-3/mitochondrial apoptosis, and initiating damaging autophagy.
{"title":"Novel platinum nanoclusters (Pt NCs) induce mitochondrial apoptosis and damaging autophagy for the treatment of osteosarcoma—from the perspective of P53 mutation status in different cell lines","authors":"Jialin Wang, Haodi Yue, Xin Huang, Hongjian Liu, Mengjun Zhang","doi":"10.1038/s41427-024-00573-5","DOIUrl":"10.1038/s41427-024-00573-5","url":null,"abstract":"This study aimed to investigate the anticancer efficacy and underlying mechanism of novel platinum nanoclusters (Pt NCs) in osteosarcoma cell lines exhibiting distinct P53 expression profiles, namely MG-63 (P53−) and U2-OS (P53+). The findings revealed that Pt NCs exerted an inhibitory effect on proliferation, migration, and colony formation while promoting apoptosis in both MG-63 (P53−) and U2-OS (P53+) cells. The inhibitory effect on the malignant characteristics of MG-63 (P53−) cells was more obvious, indicating that the potential anticancer effect of Pt NCs was not dependent on P53. Animal experiments have substantiated the in vivo anticancer properties of Pt NCs, while also revealing their lower toxicity on cells and tissues. Pt NCs possess the ability to impede cell proliferation by inducing DNA damage and arresting the cell cycle in the G1 phase and possess the ability to promote BAX/Bcl-2/Caspase-3/mitochondrial apoptosis. Pt NCs may promote mitochondrial apoptosis by promoting damaging autophagy, thereby promoting cellular demise. This study has confirmed the P53-independent anticancer impact of Pt NCs on osteosarcoma in vitro and in vivo. Pt NCs may play a therapeutic role in more sensitive MG-63 (P53−) cells by promoting DNA damage to arrest the cell cycle, stimulating BAX/Bcl-2/Caspase-3/mitochondrial apoptosis, and initiating damaging autophagy.","PeriodicalId":19382,"journal":{"name":"Npg Asia Materials","volume":"16 1","pages":"1-13"},"PeriodicalIF":8.6,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41427-024-00573-5.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143187387","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hysteresis is an inherent property of first-order transition materials that poses challenges for solid-state refrigeration applications. Extensive research has been conducted, but the intrinsic origins of hysteresis remain poorly understood. Here, we report a study of the kinetic origin of hysteresis and the enhanced barocaloric effect (BCE) in MnCoGe-based alloys with ~2% nonmagnetic In atoms. First-principles calculations demonstrate that substituting In atoms at Ge sites rather than Co sites results in a lower energy barrier, indicating a narrower hysteresis for the former. Combining neutron powder diffraction (NPD) with magnetic and calorimetric measurements completely verified the theoretical prediction. Electron local function (ELF) calculations further reveal the atomic coordination origin of regulated hysteresis due to weaker Co–Ge bonds when In atoms replace Ge, which is opposite to Co sites. Moreover, we experimentally investigate the BCE and find that although MnCo(Ge0.98In0.02) has a lower barocaloric entropy change ΔSP than does Mn(Co0.98In0.02)Ge, the reversible ΔSrev of the former is advantageous owing to a smaller hysteresis. The maximum ΔSrev of MnCo(Ge0.98In0.02) is 1.7 times greater than that of Mn(Co0.98In0.02)Ge. These results reveal the atomic-scale mechanism regulating hysteresis and provide insights into tailoring the functional properties of novel caloric refrigeration materials. First-principles calculations demonstrated that the substitution of In for Ge has a lower energy barrier for phase transition than the substitution of In for Co in MnCoGe alloys. ELF calculations further reveal the regulated hysteresis’s atomic coordination origin. This theoretical prediction is completely verified by combining neutron, magnetic and calorimetric measurements; consequently, a largely enhanced barocaloric effect has been achieved. Hysteresis is an inherent property of first-order transition materials that poses challenges for solid-state refrigeration applications. Here we report a study of the kinetic origin of hysteresis and enhanced barocaloric effect (BCE) in MnCoGe-based alloys with about 2% non-magnetic In atoms. First-principles calculations demonstrated that the substitution of In for Ge has a lower energy barrier of phase transition than the substitution of In for Co in MnCoGe alloys, indicating a narrower hysteresis for the former. Electron local function (ELF) calculations further reveal the atomic coordination origin of regulated hysteresis due to weaker Co-Ge bonds when In atoms replaced Ge, opposite to Co sites. Such theoretical prediction is completely verified by combining neutron with magnetic and calorimetric measurements, consequently strongly enhanced reversible BCE has been achieved. These results uncover the atomic-scale mechanism regulating hysteresis and provide insights for tailoring functional properties of novel caloric refrigeration materials.
{"title":"Kinetic origin of hysteresis and the strongly enhanced reversible barocaloric effect by regulating the atomic coordination environment","authors":"Zi-Bing Yu, Hou-Bo Zhou, Feng-Xia Hu, Jian-Tao Wang, Fei-Ran Shen, Lun-Hua He, Zheng-Ying Tian, Yi-Hong Gao, Bing-Jie Wang, Yuan Lin, Yue Kan, Jing Wang, Yun-Zhong Chen, Ji-Rong Sun, Tong-Yun Zhao, Bao-Gen Shen","doi":"10.1038/s41427-024-00571-7","DOIUrl":"10.1038/s41427-024-00571-7","url":null,"abstract":"Hysteresis is an inherent property of first-order transition materials that poses challenges for solid-state refrigeration applications. Extensive research has been conducted, but the intrinsic origins of hysteresis remain poorly understood. Here, we report a study of the kinetic origin of hysteresis and the enhanced barocaloric effect (BCE) in MnCoGe-based alloys with ~2% nonmagnetic In atoms. First-principles calculations demonstrate that substituting In atoms at Ge sites rather than Co sites results in a lower energy barrier, indicating a narrower hysteresis for the former. Combining neutron powder diffraction (NPD) with magnetic and calorimetric measurements completely verified the theoretical prediction. Electron local function (ELF) calculations further reveal the atomic coordination origin of regulated hysteresis due to weaker Co–Ge bonds when In atoms replace Ge, which is opposite to Co sites. Moreover, we experimentally investigate the BCE and find that although MnCo(Ge0.98In0.02) has a lower barocaloric entropy change ΔSP than does Mn(Co0.98In0.02)Ge, the reversible ΔSrev of the former is advantageous owing to a smaller hysteresis. The maximum ΔSrev of MnCo(Ge0.98In0.02) is 1.7 times greater than that of Mn(Co0.98In0.02)Ge. These results reveal the atomic-scale mechanism regulating hysteresis and provide insights into tailoring the functional properties of novel caloric refrigeration materials. First-principles calculations demonstrated that the substitution of In for Ge has a lower energy barrier for phase transition than the substitution of In for Co in MnCoGe alloys. ELF calculations further reveal the regulated hysteresis’s atomic coordination origin. This theoretical prediction is completely verified by combining neutron, magnetic and calorimetric measurements; consequently, a largely enhanced barocaloric effect has been achieved. Hysteresis is an inherent property of first-order transition materials that poses challenges for solid-state refrigeration applications. Here we report a study of the kinetic origin of hysteresis and enhanced barocaloric effect (BCE) in MnCoGe-based alloys with about 2% non-magnetic In atoms. First-principles calculations demonstrated that the substitution of In for Ge has a lower energy barrier of phase transition than the substitution of In for Co in MnCoGe alloys, indicating a narrower hysteresis for the former. Electron local function (ELF) calculations further reveal the atomic coordination origin of regulated hysteresis due to weaker Co-Ge bonds when In atoms replaced Ge, opposite to Co sites. Such theoretical prediction is completely verified by combining neutron with magnetic and calorimetric measurements, consequently strongly enhanced reversible BCE has been achieved. These results uncover the atomic-scale mechanism regulating hysteresis and provide insights for tailoring functional properties of novel caloric refrigeration materials.","PeriodicalId":19382,"journal":{"name":"Npg Asia Materials","volume":"16 1","pages":"1-14"},"PeriodicalIF":8.6,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41427-024-00571-7.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143187386","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
On-demand underwater adhesives with excellent adhesive and gentle detachment properties enable stable connections to various biomedical devices and biointerfaces and avoid the risk of harmful tissue damage upon detachment. Herein, we present a Janus hydrogel adhesive that can reversibly switch its adhesion strength, which is controlled by temperature, using a thermoresponsive polymer and mussel-inspired molecules. This thermoswitchable adhesive (TSA) hydrogel displays both strong adhesion and gentle detachment with an over 1000-fold gap in underwater adhesion strength onto glass, titanium, aluminum, and Teflon substrates when exposed to temperatures above and below the lower critical solution temperature (LCST). The adhesion switch is possibly caused by the change in toughness of the TSA hydrogels with temperature because the Janus hydrogel possesses gradient crosslinked structures. Moreover, the lowermost surface is sufficiently soft to gently detach from the substrate below the LCST. The electrode-integrated hydrogel remains on human skin, and electrical signals are continuous over 10 min above the LCST. In contrast, commercially available hydrogel electrodes quickly swell and detach from the skin. The thermoswitchability of the TSA hydrogel, with its robust adhesion and gentle detachment, offers significant potential for biomedical applications characterized by minimally invasive procedures. On-demand underwater adhesives with excellent adhesive and gentle detachment properties enable stable connections to various biomedical devices and bio-interfaces and avoid the risk of harmful tissue damage upon detachment. Herein, we present a Janus hydrogel adhesive that can reversibly switch its adhesion strength, which is controlled by temperature, using a thermoresponsive polymer and mussel-inspired molecules. This thermoswitchable adhesive hydrogel displays both strong adhesion and gentle detachment with an over 1,000-fold gap in underwater adhesion strength. The thermoswitchability of the hydrogel adhesives, with its robust adhesion and gentle detachment, offers significant potential for biomedical applications characterized by minimally invasive procedures.
{"title":"Mussel-inspired thermo-switchable underwater adhesive based on a Janus hydrogel","authors":"Hiroya Abe, Daichi Yoshihara, Soichiro Tottori, Matsuhiko Nishizawa","doi":"10.1038/s41427-024-00569-1","DOIUrl":"10.1038/s41427-024-00569-1","url":null,"abstract":"On-demand underwater adhesives with excellent adhesive and gentle detachment properties enable stable connections to various biomedical devices and biointerfaces and avoid the risk of harmful tissue damage upon detachment. Herein, we present a Janus hydrogel adhesive that can reversibly switch its adhesion strength, which is controlled by temperature, using a thermoresponsive polymer and mussel-inspired molecules. This thermoswitchable adhesive (TSA) hydrogel displays both strong adhesion and gentle detachment with an over 1000-fold gap in underwater adhesion strength onto glass, titanium, aluminum, and Teflon substrates when exposed to temperatures above and below the lower critical solution temperature (LCST). The adhesion switch is possibly caused by the change in toughness of the TSA hydrogels with temperature because the Janus hydrogel possesses gradient crosslinked structures. Moreover, the lowermost surface is sufficiently soft to gently detach from the substrate below the LCST. The electrode-integrated hydrogel remains on human skin, and electrical signals are continuous over 10 min above the LCST. In contrast, commercially available hydrogel electrodes quickly swell and detach from the skin. The thermoswitchability of the TSA hydrogel, with its robust adhesion and gentle detachment, offers significant potential for biomedical applications characterized by minimally invasive procedures. On-demand underwater adhesives with excellent adhesive and gentle detachment properties enable stable connections to various biomedical devices and bio-interfaces and avoid the risk of harmful tissue damage upon detachment. Herein, we present a Janus hydrogel adhesive that can reversibly switch its adhesion strength, which is controlled by temperature, using a thermoresponsive polymer and mussel-inspired molecules. This thermoswitchable adhesive hydrogel displays both strong adhesion and gentle detachment with an over 1,000-fold gap in underwater adhesion strength. The thermoswitchability of the hydrogel adhesives, with its robust adhesion and gentle detachment, offers significant potential for biomedical applications characterized by minimally invasive procedures.","PeriodicalId":19382,"journal":{"name":"Npg Asia Materials","volume":"16 1","pages":"1-11"},"PeriodicalIF":8.6,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41427-024-00569-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143187384","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cross-luminescence (CL) in a barium fluoride (BaF2) scintillator arising from the recombination of a valence band electron and a core band hole results in a fast picosecond decay time. However, the CL emission wavelength in the vacuum ultraviolet region is difficult to detect, and intrinsically intense and slow nanosecond self-trapped exciton (STE) luminescence occurs. Herein, we report a redshift in the CL emission wavelength with high-pressure application. The wavelength of the CL emission shifted from 221 nm to 240 nm when 5.0 GPa was applied via a sapphire anvil cell. Increasing the pressure decreases the core-valence bandgap due to the downward expansion of the valence band, resulting in a decrease in the valence band minimum. The onset of a phase transition from a cubic crystal structure to an orthorhombic crystal structure at 3.7 GPa inhibited the recombination of conduction band electrons and self-trapped holes, leading to the disappearance of the STE emission. Manipulating the band structure of BaF2 by high-pressure application enables control of its luminescence emission, providing a pathway toward solving the problems inherent in this leading fast-response scintillator. Cross-luminescence (CL) in a barium fluoride arising from the recombination of a valence band electron and a core band hole, and intrinsically intense self-trapped exciton (STE) luminescence occurs. Herein, we report a redshift in the CL emission wavelength with high-pressure application via a sapphire anvil cell. Increasing the pressure decreases the core-valence bandgap due to the downward expansion of the valence band. The onset of a phase transition from a cubic crystal structure to an orthorhombic crystal structure at 3.7 GPa inhibited the recombination of conduction band electrons and self-trapped holes, leading to the disappearance of the STE emission.
{"title":"Pressure-controlled luminescence in fast-response barium fluoride crystals","authors":"Marilou Cadatal-Raduban, Luong Viet Mui, Masahiro Yamashita, Yuki Shibazaki, Toshihiko Shimizu, Nobuhiko Sarukura, Kohei Yamanoi","doi":"10.1038/s41427-024-00570-8","DOIUrl":"10.1038/s41427-024-00570-8","url":null,"abstract":"Cross-luminescence (CL) in a barium fluoride (BaF2) scintillator arising from the recombination of a valence band electron and a core band hole results in a fast picosecond decay time. However, the CL emission wavelength in the vacuum ultraviolet region is difficult to detect, and intrinsically intense and slow nanosecond self-trapped exciton (STE) luminescence occurs. Herein, we report a redshift in the CL emission wavelength with high-pressure application. The wavelength of the CL emission shifted from 221 nm to 240 nm when 5.0 GPa was applied via a sapphire anvil cell. Increasing the pressure decreases the core-valence bandgap due to the downward expansion of the valence band, resulting in a decrease in the valence band minimum. The onset of a phase transition from a cubic crystal structure to an orthorhombic crystal structure at 3.7 GPa inhibited the recombination of conduction band electrons and self-trapped holes, leading to the disappearance of the STE emission. Manipulating the band structure of BaF2 by high-pressure application enables control of its luminescence emission, providing a pathway toward solving the problems inherent in this leading fast-response scintillator. Cross-luminescence (CL) in a barium fluoride arising from the recombination of a valence band electron and a core band hole, and intrinsically intense self-trapped exciton (STE) luminescence occurs. Herein, we report a redshift in the CL emission wavelength with high-pressure application via a sapphire anvil cell. Increasing the pressure decreases the core-valence bandgap due to the downward expansion of the valence band. The onset of a phase transition from a cubic crystal structure to an orthorhombic crystal structure at 3.7 GPa inhibited the recombination of conduction band electrons and self-trapped holes, leading to the disappearance of the STE emission.","PeriodicalId":19382,"journal":{"name":"Npg Asia Materials","volume":"16 1","pages":"1-12"},"PeriodicalIF":8.6,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41427-024-00570-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143187385","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Metal nanoparticles have extraordinary properties, but their integration into mesostructures has been challenging. Producing uniformly dispersed nanoparticles attached to substrates in industrial quantities is difficult. Herein, a “plasmashock” method was developed to synthesize metal nanoparticles anchored on different types of carbonaceous substrates using liquid salt solution precursors. These self-supporting, nanoparticle-loaded carbon fabrics are mechanically robust and have been tested as antibacterial substrates and electrocatalysts for reducing carbon dioxide and nitrite. A piece of silver–carbon nanotube paper with a silver loading of ~0.13 mg cm−2 treated after a few-second plasmashock presents good antibacterial and electrocatalytic properties in wastewater, even after 20 bactericidal immersion cycles, due to the strong bonding of the nanoparticles to the substrate. The results prove the effectiveness of this plasmashock method in creating free-standing functional composite films or membranes. A “plasmashock” method was developed to synthesize metal nanoparticles anchored on different kinds of carbonaceous substrates using liquid salt solution precursors. These self-supporting, nanoparticles-loaded carbon fabrics are mechanically robust and tested as antibacterial substrate and electrocatalysts for reducing carbon dioxide and nitrite.
{"title":"Burst plasma preparation of metallic nanoparticles on carbon fabrics for antibacterial and electrocatalytic applications","authors":"Guiyin Xu, Zheyi Meng, Yunteng Cao, Zixu Tao, Qing-Jie Li, Myles Stapelberg, Bing Han, Rui Gao, Qipeng Yu, Meng Gu, Benedetto Marelli, Hailiang Wang, Meifang Zhu, Ju Li","doi":"10.1038/s41427-024-00566-4","DOIUrl":"10.1038/s41427-024-00566-4","url":null,"abstract":"Metal nanoparticles have extraordinary properties, but their integration into mesostructures has been challenging. Producing uniformly dispersed nanoparticles attached to substrates in industrial quantities is difficult. Herein, a “plasmashock” method was developed to synthesize metal nanoparticles anchored on different types of carbonaceous substrates using liquid salt solution precursors. These self-supporting, nanoparticle-loaded carbon fabrics are mechanically robust and have been tested as antibacterial substrates and electrocatalysts for reducing carbon dioxide and nitrite. A piece of silver–carbon nanotube paper with a silver loading of ~0.13 mg cm−2 treated after a few-second plasmashock presents good antibacterial and electrocatalytic properties in wastewater, even after 20 bactericidal immersion cycles, due to the strong bonding of the nanoparticles to the substrate. The results prove the effectiveness of this plasmashock method in creating free-standing functional composite films or membranes. A “plasmashock” method was developed to synthesize metal nanoparticles anchored on different kinds of carbonaceous substrates using liquid salt solution precursors. These self-supporting, nanoparticles-loaded carbon fabrics are mechanically robust and tested as antibacterial substrate and electrocatalysts for reducing carbon dioxide and nitrite.","PeriodicalId":19382,"journal":{"name":"Npg Asia Materials","volume":"16 1","pages":"1-11"},"PeriodicalIF":8.6,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41427-024-00566-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143187401","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-27DOI: 10.1038/s41427-024-00568-2
Eun Mi Kim, Jinseok Han, Guk-Tae Kim, Huan Li, Meng Yang Cui, Ganghwan Park, Dong-Ho Baek, Bo Jin, Sang Mun Jeong, Jae-Kwang Kim
The demand for high-capacity batteries with long cycle life and safety has been increasing owing to the expanding mid-to-large battery market. Li–S batteries are suitable energy-storage devices because of their reversibility, high theoretical capacity, and inexpensive construction materials. However, their performance is limited by various factors, including the shuttle effect and dendrite growth at the anode. Here, an integrated electrode for use in all-solid-state (ASS) Li–S batteries was formed via hot pressing. In detail, S particles dispersed in a functionalized reduced graphite oxide (rGO) cathode with a binder-less polymer electrolyte (PE) and a dual-anion ionic liquid-containing cross-linked poly(ethylene oxide)–Li bis(fluoromethanesulfonyl)imide–N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide-based solid polymer electrolyte (SPE, PEO–LiFSI0.1(Pyr14TFSI)0.4) were hot-pressed into an integrated electrode, which serves as both the cathode and electrolyte. The resulting S/rGO-based solid-state Li–S batteries exhibited more stable performance than Li–S batteries using liquid electrolytes did, indicating that the dual-anion SPE layer effectively suppressed dendritic Li formation and the shuttle effect with high ionic conductivity. At 0.1 C, the battery discharge capacities were 957 and 576 mAh g−1 in the first cycle and after 100 cycles, respectively. At 1 C, the reversible capacity was 590 and 417 mAh g−1 in the first cycle and after 100 cycles, respectively (capacity retention = 71%). Therefore, the proposed S/rGO/PE//LiFSI0.1(Pyr14TFSI)0.4-integrated electrodes are beneficial for ASS Li–S batteries. Sulfur particles disperse in a functionalized reduced graphite oxide (rGO) cathode with a binder-less polymer electrolyte and a dual-anion ionic liquid-containing cross-linked PEO–LiFSI0.1(Pyr14TFSI)0.4 are hot-pressed into an integrated electrode, serving as both the cathode and electrolyte. Dual-anion solid polymer electrolyte and rGO-functional integrated sulfur electrode presents a novel method to improve the electrochemical properties of lithium-sulfur batteries.
随着中大型电池市场的扩大，对循环寿命长、安全性好的大容量电池的需求也在不断增加。锂硫电池具有可逆性、理论容量大、结构材料便宜等优点，是一种合适的储能设备。然而，它们的性能受到各种因素的限制，包括梭子效应和阳极的枝晶生长。在这里，通过热压形成了用于全固态（ASS） Li-S电池的集成电极。具体而言，S颗粒分散在功能化还原氧化石墨（rGO）阴极上，采用无粘结剂聚合物电解质（PE）和双阴离子液体(含交联聚（环氧乙烷）-锂二（氟甲烷磺酰）亚胺- n -丁基- n -甲基吡啶二（三氟甲烷磺酰）亚胺基固体聚合物电解质（SPE, PEO-LiFSI0.1 (Pyr14TFSI)0.4）热压成一个集成电极，作为阴极和电解质。结果表明，基于S/ rgo的固态锂电池性能比使用液体电解质的锂电池更稳定，这表明双阴离子SPE层有效抑制了枝晶锂的形成和高离子电导率的穿梭效应。在0.1 C下，第一次循环和100次循环后，电池的放电容量分别为957和576 mAh g−1。在1℃下，第一次循环和100次循环后的可逆容量分别为590和417 mAh g - 1（容量保持率为71%）。因此，所提出的S/rGO/PE//LiFSI0.1(Pyr14TFSI)0.4集成电极有利于ASS Li-S电池。硫颗粒分散在功能化还原氧化石墨（rGO）阴极中，采用无粘结剂聚合物电解质和含有交联PEO-LiFSI0.1 (Pyr14TFSI)0.4的双阴离子液体，热压成集成电极，同时充当阴极和电解质。双阴离子固体聚合物电解质和rgo功能集成硫电极是改善锂硫电池电化学性能的新方法。
{"title":"Sulfur/reduced graphite oxide and dual-anion solid polymer‒electrolyte integrated structure for high-loading practical all-solid-state lithium–sulfur batteries","authors":"Eun Mi Kim, Jinseok Han, Guk-Tae Kim, Huan Li, Meng Yang Cui, Ganghwan Park, Dong-Ho Baek, Bo Jin, Sang Mun Jeong, Jae-Kwang Kim","doi":"10.1038/s41427-024-00568-2","DOIUrl":"10.1038/s41427-024-00568-2","url":null,"abstract":"The demand for high-capacity batteries with long cycle life and safety has been increasing owing to the expanding mid-to-large battery market. Li–S batteries are suitable energy-storage devices because of their reversibility, high theoretical capacity, and inexpensive construction materials. However, their performance is limited by various factors, including the shuttle effect and dendrite growth at the anode. Here, an integrated electrode for use in all-solid-state (ASS) Li–S batteries was formed via hot pressing. In detail, S particles dispersed in a functionalized reduced graphite oxide (rGO) cathode with a binder-less polymer electrolyte (PE) and a dual-anion ionic liquid-containing cross-linked poly(ethylene oxide)–Li bis(fluoromethanesulfonyl)imide–N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide-based solid polymer electrolyte (SPE, PEO–LiFSI0.1(Pyr14TFSI)0.4) were hot-pressed into an integrated electrode, which serves as both the cathode and electrolyte. The resulting S/rGO-based solid-state Li–S batteries exhibited more stable performance than Li–S batteries using liquid electrolytes did, indicating that the dual-anion SPE layer effectively suppressed dendritic Li formation and the shuttle effect with high ionic conductivity. At 0.1 C, the battery discharge capacities were 957 and 576 mAh g−1 in the first cycle and after 100 cycles, respectively. At 1 C, the reversible capacity was 590 and 417 mAh g−1 in the first cycle and after 100 cycles, respectively (capacity retention = 71%). Therefore, the proposed S/rGO/PE//LiFSI0.1(Pyr14TFSI)0.4-integrated electrodes are beneficial for ASS Li–S batteries. Sulfur particles disperse in a functionalized reduced graphite oxide (rGO) cathode with a binder-less polymer electrolyte and a dual-anion ionic liquid-containing cross-linked PEO–LiFSI0.1(Pyr14TFSI)0.4 are hot-pressed into an integrated electrode, serving as both the cathode and electrolyte. Dual-anion solid polymer electrolyte and rGO-functional integrated sulfur electrode presents a novel method to improve the electrochemical properties of lithium-sulfur batteries.","PeriodicalId":19382,"journal":{"name":"Npg Asia Materials","volume":"16 1","pages":"1-13"},"PeriodicalIF":8.6,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41427-024-00568-2.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143187400","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The charge density wave (CDW), as a hallmark of vanadium-based kagome superconductor AV3Sb5 (A = K, Rb, Cs), has attracted intensive attention. However, the fundamental controversy regarding the underlying mechanism of CDW therein persists. Recently, the vanadium-based bi-layered kagome metal ScV6Sn6, reported to exhibit a long-range charge order below 94 K, has emerged as a promising candidate to further clarify this core issue. Here, employing micro-focusing angle-resolved photoemission spectroscopy (μ-ARPES) and first-principles calculations, we systematically studied the unique CDW order in vanadium-based bi-layered kagome metals by comparing ScV6Sn6 with its isostructural counterpart YV6Sn6, which lacks a CDW ground state. Combining ARPES data and the corresponding joint density of states (DOS), we suggest that the VHS nesting mechanism might be invalid in these materials. Besides, in ScV6Sn6, we identified multiple hybridization energy gaps resulting from CDW-induced band folding, along with an anomalous band dispersion, implying a potential electron-phonon coupling-driven mechanism underlying the formation of the CDW order. Our finding not only comprehensively maps the electronic structure of V-based bi-layer kagome metals but also provides constructive experimental evidence for the unique origin of CDW in this system. We investigated the origins of charge density wave (CDW) mechanisms in the bi-layered kagome metal ScV6Sn6 by comparing its electronic structure with that of its isostructural counterpart YV6Sn6, which does not exhibit a CDW state. Our ARPES measurements reveal that the Van Hove singularity (VHS) nesting mechanism may not be valid in the CDW state. In ScV6Sn6, the electronic structure shows a CDW-induced band gap accompanied by anomalous band dispersion near the M point of the Brillouin zone. These findings provide experimental evidence for the origin of CDW in vanadium-based kagome metals.
{"title":"Unveiling the charge density wave mechanism in vanadium-based Bi-layered kagome metals","authors":"Yi-Chen Yang, Soohyun Cho, Tong-Rui Li, Xiang-Qi Liu, Zheng-Tai Liu, Zhi-Cheng Jiang, Jian-Yang Ding, Wei Xia, Zi-Cheng Tao, Jia-Yu Liu, Wen-Chuan Jing, Yu Huang, Yu-Ming Shi, Soonsang Huh, Takeshi Kondo, Zhe Sun, Ji-Shan Liu, Mao Ye, Yi-Lin Wang, Yan-Feng Guo, Da-Wei Shen","doi":"10.1038/s41427-024-00567-3","DOIUrl":"10.1038/s41427-024-00567-3","url":null,"abstract":"The charge density wave (CDW), as a hallmark of vanadium-based kagome superconductor AV3Sb5 (A = K, Rb, Cs), has attracted intensive attention. However, the fundamental controversy regarding the underlying mechanism of CDW therein persists. Recently, the vanadium-based bi-layered kagome metal ScV6Sn6, reported to exhibit a long-range charge order below 94 K, has emerged as a promising candidate to further clarify this core issue. Here, employing micro-focusing angle-resolved photoemission spectroscopy (μ-ARPES) and first-principles calculations, we systematically studied the unique CDW order in vanadium-based bi-layered kagome metals by comparing ScV6Sn6 with its isostructural counterpart YV6Sn6, which lacks a CDW ground state. Combining ARPES data and the corresponding joint density of states (DOS), we suggest that the VHS nesting mechanism might be invalid in these materials. Besides, in ScV6Sn6, we identified multiple hybridization energy gaps resulting from CDW-induced band folding, along with an anomalous band dispersion, implying a potential electron-phonon coupling-driven mechanism underlying the formation of the CDW order. Our finding not only comprehensively maps the electronic structure of V-based bi-layer kagome metals but also provides constructive experimental evidence for the unique origin of CDW in this system. We investigated the origins of charge density wave (CDW) mechanisms in the bi-layered kagome metal ScV6Sn6 by comparing its electronic structure with that of its isostructural counterpart YV6Sn6, which does not exhibit a CDW state. Our ARPES measurements reveal that the Van Hove singularity (VHS) nesting mechanism may not be valid in the CDW state. In ScV6Sn6, the electronic structure shows a CDW-induced band gap accompanied by anomalous band dispersion near the M point of the Brillouin zone. These findings provide experimental evidence for the origin of CDW in vanadium-based kagome metals.","PeriodicalId":19382,"journal":{"name":"Npg Asia Materials","volume":"16 1","pages":"1-9"},"PeriodicalIF":8.6,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41427-024-00567-3.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143187399","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-13DOI: 10.1038/s41427-024-00565-5
Zhendong Li, Xinxin Wang, Kexin Zeng, Zichao Guo, Chong Li, Xiang Yu, Seeram Ramakrishna, Zhonggang Wang, Yang Lu
In practical engineering, noise and impact hazards are pervasive, indicating the pressing demand for materials that can absorb both sound and stress wave energy simultaneously. However, the rational design of such multifunctional materials remains a challenge. Herein, inspired by cuttlebone, we present bioinspired architected metamaterials with unprecedented sound-absorbing and mechanical properties engineered via a weakly-coupled design. The acoustic elements feature heterogeneous multilayered resonators, whereas the mechanical responses are based on asymmetric cambered cell walls. These metamaterials experimentally demonstrated an average absorption coefficient of 0.80 from 1.0 to 6.0 kHz, with 77% of the data points exceeding the desired 0.75 threshold, all with a compact 21 mm thickness. An absorptance-thickness map is devised for assessing the sound-absorption efficiency. The high-fidelity microstructure-based model reveals the air friction damping mechanism, with broadband behavior attributed to multimodal hybrid resonance. Empowered by the cambered design of cell walls, metamaterials shift catastrophic failure toward a progressive deformation mode characterized by stable stress plateaus and ultrahigh specific energy absorption of 50.7 J/g—a 558.4% increase over the straight-wall design. After the deformation mechanisms are elucidated, a comprehensive research framework for burgeoning acousto-mechanical metamaterials is proposed. Overall, our study broadens the horizon for multifunctional material design. Noise and impact hazards are pervasive in engineering, necessitating materials capable of absorbing both sound and stress wave energy. Here, we present bioinspired metamaterials with exceptional sound-absorbing and mechanical properties using a weakly-coupled design strategy. These materials incorporate multi-layered resonators for superior acoustic performance and cambered cell walls for enhanced structural strength. They achieve an average absorption coefficient of 0.80 across the 1.0 to 6.0 kHz range, all within a sleek 21 mm thickness. Furthermore, the design transitions failure modes from catastrophic to progressive, resulting in a remarkable 558.4% increase in energy absorption compared to conventional designs.
{"title":"Unprecedented mechanical wave energy absorption observed in multifunctional bioinspired architected metamaterials","authors":"Zhendong Li, Xinxin Wang, Kexin Zeng, Zichao Guo, Chong Li, Xiang Yu, Seeram Ramakrishna, Zhonggang Wang, Yang Lu","doi":"10.1038/s41427-024-00565-5","DOIUrl":"10.1038/s41427-024-00565-5","url":null,"abstract":"In practical engineering, noise and impact hazards are pervasive, indicating the pressing demand for materials that can absorb both sound and stress wave energy simultaneously. However, the rational design of such multifunctional materials remains a challenge. Herein, inspired by cuttlebone, we present bioinspired architected metamaterials with unprecedented sound-absorbing and mechanical properties engineered via a weakly-coupled design. The acoustic elements feature heterogeneous multilayered resonators, whereas the mechanical responses are based on asymmetric cambered cell walls. These metamaterials experimentally demonstrated an average absorption coefficient of 0.80 from 1.0 to 6.0 kHz, with 77% of the data points exceeding the desired 0.75 threshold, all with a compact 21 mm thickness. An absorptance-thickness map is devised for assessing the sound-absorption efficiency. The high-fidelity microstructure-based model reveals the air friction damping mechanism, with broadband behavior attributed to multimodal hybrid resonance. Empowered by the cambered design of cell walls, metamaterials shift catastrophic failure toward a progressive deformation mode characterized by stable stress plateaus and ultrahigh specific energy absorption of 50.7 J/g—a 558.4% increase over the straight-wall design. After the deformation mechanisms are elucidated, a comprehensive research framework for burgeoning acousto-mechanical metamaterials is proposed. Overall, our study broadens the horizon for multifunctional material design. Noise and impact hazards are pervasive in engineering, necessitating materials capable of absorbing both sound and stress wave energy. Here, we present bioinspired metamaterials with exceptional sound-absorbing and mechanical properties using a weakly-coupled design strategy. These materials incorporate multi-layered resonators for superior acoustic performance and cambered cell walls for enhanced structural strength. They achieve an average absorption coefficient of 0.80 across the 1.0 to 6.0 kHz range, all within a sleek 21 mm thickness. Furthermore, the design transitions failure modes from catastrophic to progressive, resulting in a remarkable 558.4% increase in energy absorption compared to conventional designs.","PeriodicalId":19382,"journal":{"name":"Npg Asia Materials","volume":"16 1","pages":"1-14"},"PeriodicalIF":8.6,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41427-024-00565-5.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142216206","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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