The ideal composite electrolyte for the pursued safe and high-energy-density lithium metal batteries(LMBs)is expected to demonstrate peculiarity of superior bulk conductivity,low interfacial resistances,and good compa...The ideal composite electrolyte for the pursued safe and high-energy-density lithium metal batteries(LMBs)is expected to demonstrate peculiarity of superior bulk conductivity,low interfacial resistances,and good compatibility against both Li-metal anode and high-voltage cathode.There is no composite electrolyte to synchronously meet all these requirements yet,and the battery performance is inhibited by the absence of effective electrolyte design.Here we report a unique"concentrated ionogel-in-ceramic"silanization composite electrolyte(SCE)and validate an electrolyte design strategy based on the coupling of high-content silane-conditioning garnet and concentrated ionogel that builds well-percolated Li+transport pathways and tackles the interface issues to respond all the aforementioned requirements.It is revealed that the silane conditioning enables the uniform dispersion of garnet nanoparticles at high content(70 wt%)and forms mixed-lithiophobic-conductive LiF-Li3N solid electrolyte interphase.Notably,the yielding SCE delivers an ultrahigh ionic conductivity of 1.76 X 10^(-3)S cm^(-1)at 25℃,an extremely low Li-metal/electrolyte interfacial area-specific resistance of 13Ωcm^(2),and a distinctly excellent long-term 1200 cycling without any capacity decay in 4.3 V Li‖LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(NCM523)quasi-solid-state LMB.This composite electrolyte design strategy can be extended to other quasi-/solid-state LMBs.展开更多
Porous mullite hollow fiber membranes were prepared with a combined phase-inversion and sintering method,using three sintering additives including yttrium stabilized zirconia(YSZ),small mullite particles(SMP),and tita...Porous mullite hollow fiber membranes were prepared with a combined phase-inversion and sintering method,using three sintering additives including yttrium stabilized zirconia(YSZ),small mullite particles(SMP),and titanium oxide(TiO2)to promote the particle sintering.The results indicated that all the three additives could improve the sintering performance of mullite hollow fiber membranes due to the decrease in activation energy of mullite grains.Both YSZ and T i02 could react with mullite grains to generate composite oxides(e.g.,ZrSi04 and Al2Ti05)during sintering,following a reaction-sintering mechanism.Interestingly,the newly generated ZrSiO4 was instable and further decomposed into monoclinic ZrO2 and SiO2 in the sintering process.The decomposition could avoid excessive embedment of composite oxides among mullite grains which have negative impact on mechanical strength of mullite hollow fibers.Overall,the doping of YSZ provided a better promotion effect on the sintering of mullite hollow fiber membranes,where the microstructural and mechanical properties are insensitive to the doping content and sintering temperatures,so it could be used as the candidate for the large-scale preparation of mullite hollow fibers.展开更多
基金supported by the Key Program for International Science and Technology Cooperation Projects of the Ministry of Science and Technology of China(2021YFE0109700)Technical Innovation and Application Development Project of Chongqing(Z20230084)+7 种基金Opening Project of State Key Laboratory of High Performance Ceramics and Superfine Microstructure(SKL202106SIC)Chinese National Natural Science Fund(11632004,U1864208)National Science and Technology Major Project(2017-VII-0011-0106)Science and Technology Planning Project of Tianjin(20ZYJDJC00030)Key Program of Research and Development of Hebei Province(202030507040009)Fund for Innovative Research Groups of Natural Science Foundation of Hebei Province(A2020202002)Natural Science Foundation of Chongqing(cstc2021jcyjmsxm X0241)Key Project of Natural Science Foundation of Tianjin(S20ZDF077)
文摘The ideal composite electrolyte for the pursued safe and high-energy-density lithium metal batteries(LMBs)is expected to demonstrate peculiarity of superior bulk conductivity,low interfacial resistances,and good compatibility against both Li-metal anode and high-voltage cathode.There is no composite electrolyte to synchronously meet all these requirements yet,and the battery performance is inhibited by the absence of effective electrolyte design.Here we report a unique"concentrated ionogel-in-ceramic"silanization composite electrolyte(SCE)and validate an electrolyte design strategy based on the coupling of high-content silane-conditioning garnet and concentrated ionogel that builds well-percolated Li+transport pathways and tackles the interface issues to respond all the aforementioned requirements.It is revealed that the silane conditioning enables the uniform dispersion of garnet nanoparticles at high content(70 wt%)and forms mixed-lithiophobic-conductive LiF-Li3N solid electrolyte interphase.Notably,the yielding SCE delivers an ultrahigh ionic conductivity of 1.76 X 10^(-3)S cm^(-1)at 25℃,an extremely low Li-metal/electrolyte interfacial area-specific resistance of 13Ωcm^(2),and a distinctly excellent long-term 1200 cycling without any capacity decay in 4.3 V Li‖LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(NCM523)quasi-solid-state LMB.This composite electrolyte design strategy can be extended to other quasi-/solid-state LMBs.
基金the National Natural Science Foundation of China(22035002,21776128,21878147,21808106)National Key Research and Development Project(2018YFE0118200)+2 种基金the Leading Talent in Ten-Thousand Talent Program(2019)"333 Talent Project"of Jiangsu Province,the Young Fund of Jiangsu Province(BK20170132)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Porous mullite hollow fiber membranes were prepared with a combined phase-inversion and sintering method,using three sintering additives including yttrium stabilized zirconia(YSZ),small mullite particles(SMP),and titanium oxide(TiO2)to promote the particle sintering.The results indicated that all the three additives could improve the sintering performance of mullite hollow fiber membranes due to the decrease in activation energy of mullite grains.Both YSZ and T i02 could react with mullite grains to generate composite oxides(e.g.,ZrSi04 and Al2Ti05)during sintering,following a reaction-sintering mechanism.Interestingly,the newly generated ZrSiO4 was instable and further decomposed into monoclinic ZrO2 and SiO2 in the sintering process.The decomposition could avoid excessive embedment of composite oxides among mullite grains which have negative impact on mechanical strength of mullite hollow fibers.Overall,the doping of YSZ provided a better promotion effect on the sintering of mullite hollow fiber membranes,where the microstructural and mechanical properties are insensitive to the doping content and sintering temperatures,so it could be used as the candidate for the large-scale preparation of mullite hollow fibers.