Solid-state electrolytes(SSEs),which replace flammable and toxic liquid electrolytes,have attracted widely attention.However,there exist still some challenges in actual application such as poor interfacial compatibili...Solid-state electrolytes(SSEs),which replace flammable and toxic liquid electrolytes,have attracted widely attention.However,there exist still some challenges in actual application such as poor interfacial compatibility and slow ionic migration.In this study,Mg O nanofibers and MgF;nanofibers were prepared via the electro-blow spinning and high-temperature calcination methods,and were applied to all-solid-state lithium metal batteries for the first time.The organic-inorganic composite SSEs exhibited continuous conduction paths based on the virtue of the nanofibers with high length-to-diameter ratio,which were designed and prepared by mixing prepared fillers into the poly(ethylene oxide)(PEO)/lithium bis(trifluoromethane)sulfonilimide(Li TFSI)system.The effect of filler with different morphologies,doping ratios and component on ionic conductivity,electrochemical stability and cycle performance were explored under two kinds of[EO]/[Li^(+)]ratios and ambient temperatures.The ionic conductivities of electrolytes containing Mg O and MgF;nanofibers can reach up to 1.19×10^(-4) and 1.39×10^(-4) S cm^(-1) at 30℃,respectively.They were attributed to specific ionic conductive enhancement at the organicinorganic interface,reduced crystallinity and Lewis acid interaction,which can effectively promote the dissociation of the lithium salts.Especially MgF_(2) nanofiber,combining low electronic conductance,excellent electrochemical stability and outstanding inhibition for lithium dendrites of fluorides,endowed the battery with an initial specific capacity of 140.6 m Ah g^(-1) and capacity decay rate per cycle of 0.055%after500 cycles at 50℃.The work can provide an idea to design SSE with fast and multi-dimensional Li conductive paths and excellent interfacial compatibility.展开更多
Lithium metal batteries assembled with solid-state electrolyte can offer high safety and volumetric energy density compared to liquid electrolyte.The polymer solid-state electrolytes of poly(ethylene oxide)(PEO)are wi...Lithium metal batteries assembled with solid-state electrolyte can offer high safety and volumetric energy density compared to liquid electrolyte.The polymer solid-state electrolytes of poly(ethylene oxide)(PEO)are widely used in lithium metal solid-state batteries due to their unique properties.However,there are still some defects such as low ionic conductivity at room temperature and weak inhibition of lithium dendrite growth.Herein,the spiny inorganic nanofibers heterostructure with mullite whiskers grown on the surface of aluminum fluoride(AlF_(3))nanofibers are introduced into the PEOLi TFSI electrolytes for the first time to prepare composite solid-state electrolytes.The AlF_(3)as a strong Lewis acid can adsorb anions and promote the dissociation of Li salts.Besides,the specially threedimensional(3D)structure enlarges the effective contacting interface with the PEO polymer,which allows the lithium ions to be transported not only along the large aspect ratio of AlF3nanofibers,but also along the mullite phase in the transmembrane direction rapidly.Thereby,the transport channel of lithium ions at the spiny inorganic nanofibers-polymer interface is further improved.Benefiting from these advantages,the obtained composite solid-state electrolyte has a high ionic conductivity of 1.58×10^(-4)S cm^(-1)at 30℃and the lithium ions transfer number of 0.53.In addition,the AlF3has strong binding energy with anions,low electronic conductivity and wide electrochemical stability window,and reduced nucleation overpotential of lithium during cycling,which is positive for lithium dendrite suppression in solid-state electrolytes.Thus,the assembled symmetric Li/Li symmetric batteries exhibit stable cycling performance at different area capacities of 0.15,0.2,0.3 and 0.4 m A h cm^(-2).More importantly,the LiFePO_(4)(LFP)/Li battery still has 113.5 m A h g-1remaining after 400 cycles at 50℃and the Coulomb efficiency is nearly 100%during the long cycle.Overall,the interconnected structure of 3D spiny inorganic heterostructure nanofiber constitutes fast and uninterrupted lithium ions transport channels,maximizing the synergistic effect of interfacial transport of inorganic fillers and reducing PEO crystallinity,thus providing a novel approach to high performance solid-state electrolytes.展开更多
Developing free-standing and mechanical robust membrane materials capable of superior enrichment of phosphopeptides for analyzing and identifying the specific phosphoproteome of cancer cells is significant in understa...Developing free-standing and mechanical robust membrane materials capable of superior enrichment of phosphopeptides for analyzing and identifying the specific phosphoproteome of cancer cells is significant in understanding the molecular mechanisms of cancer development and exploring new therapeutic approaches,but still a significant challenge in materials design.To this end,we firstly constructed highly flexible ZrTiO_(4) nanofibrous membranes(NFMs)with excellent mechanical stability through a cost-effective and scalable electrospinning and subsequent calcination technique.Then,to further increase the enrichment capacity of the phosphopeptide,the biomimetic TiO_(2)@ZrTiO_(4) NFMs with root hair or leaf like branch microstructure are developed by the hydrothermal post-synthetic modification of ZrTiO_(4) NFMs through growing unfurling TiO_(2) nanosheets onto the ZrTiO_(4) nanofibers.Importantly,remarkable flexibility and mechanical stability enable the resulting TiO_(2)@ZrTiO_(4) NFMs excellent practicability,while the biomimetic microstructure allows it outstanding enrichment ability of the phosphopeptide and identification ability of the specific phosphoproteins in the digest of cervical cancer cells.Specifically,6770 phosphopeptides can be enriched by TiO_(2)@ZrTiO_(4) NFMs(2205 corresponding phosphoproteins can be identified),and the value is much higher than that of ZrTiO_(4) NFMs(6399 phosphopeptides and 2132 identified phosphoproteins)and commercial high-performance TiO_(2) particles(4525 phosphopeptides and 1811 identified phosphoproteins).These results demonstrate the super ability of TiO_(2)@ZrTiO_(4) NFMs in phosphopeptide enrichment and great potential for exploring the pathogenesis of cancer.展开更多
基金supported by the National Natural Science Foundation of China(grant No.51973157)the Special Grade of the Financial Support from the China Postdoctoral Science Foundation(grant No.2020T130469)+2 种基金the Tianjin Municipal University Students’Innovation and Entrepreneurship Training Program Project(grant No.201910058036)the Science and Technology Plans of Tianjin(grant No.19PTSYJC00010)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(grant No.2018KJ196)。
文摘Solid-state electrolytes(SSEs),which replace flammable and toxic liquid electrolytes,have attracted widely attention.However,there exist still some challenges in actual application such as poor interfacial compatibility and slow ionic migration.In this study,Mg O nanofibers and MgF;nanofibers were prepared via the electro-blow spinning and high-temperature calcination methods,and were applied to all-solid-state lithium metal batteries for the first time.The organic-inorganic composite SSEs exhibited continuous conduction paths based on the virtue of the nanofibers with high length-to-diameter ratio,which were designed and prepared by mixing prepared fillers into the poly(ethylene oxide)(PEO)/lithium bis(trifluoromethane)sulfonilimide(Li TFSI)system.The effect of filler with different morphologies,doping ratios and component on ionic conductivity,electrochemical stability and cycle performance were explored under two kinds of[EO]/[Li^(+)]ratios and ambient temperatures.The ionic conductivities of electrolytes containing Mg O and MgF;nanofibers can reach up to 1.19×10^(-4) and 1.39×10^(-4) S cm^(-1) at 30℃,respectively.They were attributed to specific ionic conductive enhancement at the organicinorganic interface,reduced crystallinity and Lewis acid interaction,which can effectively promote the dissociation of the lithium salts.Especially MgF_(2) nanofiber,combining low electronic conductance,excellent electrochemical stability and outstanding inhibition for lithium dendrites of fluorides,endowed the battery with an initial specific capacity of 140.6 m Ah g^(-1) and capacity decay rate per cycle of 0.055%after500 cycles at 50℃.The work can provide an idea to design SSE with fast and multi-dimensional Li conductive paths and excellent interfacial compatibility.
基金supported by the National Natural Science Foundation of China(51973157,61904123,52103061,52203066)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(2018KJ196)+3 种基金the project funded by China Postdoctoral Science Foundation(2021T140419)Tianjin Municipal College Student’Innovation and Entrepreneurship Training Program(202110058052)the National Innovation and Entrepreneurship Training Program for College Students(202110058017)the State Key Laboratory of Membrane and Membrane Separation,Tiangong University。
文摘Lithium metal batteries assembled with solid-state electrolyte can offer high safety and volumetric energy density compared to liquid electrolyte.The polymer solid-state electrolytes of poly(ethylene oxide)(PEO)are widely used in lithium metal solid-state batteries due to their unique properties.However,there are still some defects such as low ionic conductivity at room temperature and weak inhibition of lithium dendrite growth.Herein,the spiny inorganic nanofibers heterostructure with mullite whiskers grown on the surface of aluminum fluoride(AlF_(3))nanofibers are introduced into the PEOLi TFSI electrolytes for the first time to prepare composite solid-state electrolytes.The AlF_(3)as a strong Lewis acid can adsorb anions and promote the dissociation of Li salts.Besides,the specially threedimensional(3D)structure enlarges the effective contacting interface with the PEO polymer,which allows the lithium ions to be transported not only along the large aspect ratio of AlF3nanofibers,but also along the mullite phase in the transmembrane direction rapidly.Thereby,the transport channel of lithium ions at the spiny inorganic nanofibers-polymer interface is further improved.Benefiting from these advantages,the obtained composite solid-state electrolyte has a high ionic conductivity of 1.58×10^(-4)S cm^(-1)at 30℃and the lithium ions transfer number of 0.53.In addition,the AlF3has strong binding energy with anions,low electronic conductivity and wide electrochemical stability window,and reduced nucleation overpotential of lithium during cycling,which is positive for lithium dendrite suppression in solid-state electrolytes.Thus,the assembled symmetric Li/Li symmetric batteries exhibit stable cycling performance at different area capacities of 0.15,0.2,0.3 and 0.4 m A h cm^(-2).More importantly,the LiFePO_(4)(LFP)/Li battery still has 113.5 m A h g-1remaining after 400 cycles at 50℃and the Coulomb efficiency is nearly 100%during the long cycle.Overall,the interconnected structure of 3D spiny inorganic heterostructure nanofiber constitutes fast and uninterrupted lithium ions transport channels,maximizing the synergistic effect of interfacial transport of inorganic fillers and reducing PEO crystallinity,thus providing a novel approach to high performance solid-state electrolytes.
基金supported by the National Natural Science Foundation of China(Nos.52202110,22201167)the Natural Science Foundation of Science and Technology Agency of Shanxi Province(No.20210302124654)+6 种基金the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(No.2021L259)the Innovation and Entrepreneurship Training Program for College students in Shanxi Province(No.20220312)the Outstanding Young Talents of Shaanxi Universities(2019)the Scientific and Technological Plan Project of Xi’an(No.21XJZZ0012)the Key Research and Development Program of Shaanxi Province of China(No.2022SF-201)the Service Local Special Program of Education Department of Shaanxi Province(No.23JC029)the Scientific and Technological Plan Project of the Beilin District of Xi’an City(No.GX2206).
文摘Developing free-standing and mechanical robust membrane materials capable of superior enrichment of phosphopeptides for analyzing and identifying the specific phosphoproteome of cancer cells is significant in understanding the molecular mechanisms of cancer development and exploring new therapeutic approaches,but still a significant challenge in materials design.To this end,we firstly constructed highly flexible ZrTiO_(4) nanofibrous membranes(NFMs)with excellent mechanical stability through a cost-effective and scalable electrospinning and subsequent calcination technique.Then,to further increase the enrichment capacity of the phosphopeptide,the biomimetic TiO_(2)@ZrTiO_(4) NFMs with root hair or leaf like branch microstructure are developed by the hydrothermal post-synthetic modification of ZrTiO_(4) NFMs through growing unfurling TiO_(2) nanosheets onto the ZrTiO_(4) nanofibers.Importantly,remarkable flexibility and mechanical stability enable the resulting TiO_(2)@ZrTiO_(4) NFMs excellent practicability,while the biomimetic microstructure allows it outstanding enrichment ability of the phosphopeptide and identification ability of the specific phosphoproteins in the digest of cervical cancer cells.Specifically,6770 phosphopeptides can be enriched by TiO_(2)@ZrTiO_(4) NFMs(2205 corresponding phosphoproteins can be identified),and the value is much higher than that of ZrTiO_(4) NFMs(6399 phosphopeptides and 2132 identified phosphoproteins)and commercial high-performance TiO_(2) particles(4525 phosphopeptides and 1811 identified phosphoproteins).These results demonstrate the super ability of TiO_(2)@ZrTiO_(4) NFMs in phosphopeptide enrichment and great potential for exploring the pathogenesis of cancer.