Solid polymer electrolytes have been considered as the promising candidates to improve the safety and stability of high-energy lithium metal batteries.However,the practical applications of solid polymer electrolytes a...Solid polymer electrolytes have been considered as the promising candidates to improve the safety and stability of high-energy lithium metal batteries.However,the practical applications of solid polymer electrolytes are still limited by the low ionic conductivity,poor interfacial contact with electrodes,narrow electrochemical window and weak mechanical strength.Here,a series of novel block copolymer electrolytes with three-dimensional networks are designed by cross-linked copolymerization of the polyethylene glycol soft segments and hexamethylene diisocyanate trimer hard segments.Their ionic migration performances and interface compatibilities with Li metal anode have been optimized delicately by tailoring the ratio of these functional units.The optimized block copolymer electrolyte has shown an amorphous crystalline structure,a high ionic conductivity of ~5.7×10^(-4)S cm^(-1),high lithium ion transference number(~0.49),wide electrochemical window up to ~4.65 V(vs.Li+/Li) and favorable mechanical strength at 55℃.Furthermore,the enhanced interface compatibility can well support the normal operations of lithium metal batteries using both LiFePO4 and LiNi0.8Co0.15Al0.05O2 cathodes.This study not only paves a new way to develop solid polymer electrolyte with optimizing functional units,but also provides a polymer electrolyte design strategy for the application demand of lithium metal battery.展开更多
The lithium-sulfur(Li-S)battery is one of the most promising substitutes for current energy storage systems because of its low cost,high theoretical capacity,and high energy density.However,the high solubility of inte...The lithium-sulfur(Li-S)battery is one of the most promising substitutes for current energy storage systems because of its low cost,high theoretical capacity,and high energy density.However,the high solubility of intermediate products(i.e.,lithium polysulfides)and the resultant shuttle effect lead to rapidly fading capacity and a low coulombic efficiency,which hinder the practical application of Li-S batteries.In this study,block copolymers are constructed with both an ethylene oxide unit and a styrene unit and then used as binders for Li-S batteries.Electrochemical performance improvements are attributed to the synergistic effects contributed by the different units of the block copolymer.The ethylene oxide unit traps polysulfide,which bonds strongly with the intermediate lithium polysulfide,and enhances the transport of lithium ions to reach high capacity.Meanwhile,the styrene unit maintains cathode integrity by improving the mechanical properties and elasticity of the constructed block copolymer to accommodate the large volume changes.By enabling multiple functions via different units in the polymer chain,high sulfur utilization is achieved,polysulfide diffusion is confined,and the shuttle effect is suppressed during the cycle life of Li-S batteries,as revealed by operando ultraviolet-visible spectroscopy and S Kedge X-ray absorption spectroscopy.展开更多
We investigated phase transitions in a diblock copolymer–homopolymer hybrid system blended with nanorods(NRs)by using the time-dependent Ginzburg–Landau theory.We systematically studied the effects of the number,len...We investigated phase transitions in a diblock copolymer–homopolymer hybrid system blended with nanorods(NRs)by using the time-dependent Ginzburg–Landau theory.We systematically studied the effects of the number,length and infiltration properties of the NRs on the self-assembly of the composites and the phase transitions occurring in the material.An analysis of the phase diagram was carried out to obtain the formation conditions of sea island structure nanorodbased aggregate,sea island structure nanorod-based dispersion,lamellar structure nanorod-based multilayer arrangement and nanowire structure.Further analysis of the evolution of the domain sizes and the distribution of the nanorod angle microphase structure was performed.Our simulation provides theoretical guidance for the preparation of ordered nanowire structures and a reference to improve the function of a polymer nanocomposite material.展开更多
We investigate the microphase transition of asymmetric diblock copolymer induced by nanorods of different properties using cell dynamics simulation and Brown dynamics.The results show the phase diagram and representat...We investigate the microphase transition of asymmetric diblock copolymer induced by nanorods of different properties using cell dynamics simulation and Brown dynamics.The results show the phase diagram and representative nanostructures of the diblock copolymer nanocomposite.Various structures such as sea-island structure(SI),sea-island and lamellar structure(SI-L),and lamellar structure(L) are observed in the phase diagram.The system undergoes phase transition from SI-L to SI or from L to SI with increasing length of A-like sites for all numbers of nanorods except 10 and 300,and from SI to L with increasing number of nanorods for all lengths of A-like sites.Notably,the polymer system transforms from a tilted layered structure to a parallel lamellar,perpendicular lamellar,and subsequently sea-island structure with increasing length of A-like sites for a rod number of 240.To gain more detailed insight into these structural formation mechanisms,we analyze the evolution kinetics of the system with various lengths of A-like sites of the rods.The pattern evolution and domain growth of the ordered parallel/perpendicular lamellar structure are also investigated.Furthermore,the effects of the wetting strength,rod-rod interaction,polymerization degree,and length of nanorods on the self-assembled structure of asymmetric diblock copolymer/nanorods are studied.Our simulations provide theoretical guidance on the construction of complex-assembled structures and the design of novel functional materials.展开更多
基金supported financially by the National Key R&D Program of China (Grant No. 2018YFB0104300)Beijing Natural Science Foundation (JQ19003, KZ201910005002 and L182009)+1 种基金National Natural Science Foundation of China (Grants 21875007, 51622202, and 21974007)the Project of Youth Talent Plan of Beijing Municipal Education Commission (CIT&TCD201804013)。
文摘Solid polymer electrolytes have been considered as the promising candidates to improve the safety and stability of high-energy lithium metal batteries.However,the practical applications of solid polymer electrolytes are still limited by the low ionic conductivity,poor interfacial contact with electrodes,narrow electrochemical window and weak mechanical strength.Here,a series of novel block copolymer electrolytes with three-dimensional networks are designed by cross-linked copolymerization of the polyethylene glycol soft segments and hexamethylene diisocyanate trimer hard segments.Their ionic migration performances and interface compatibilities with Li metal anode have been optimized delicately by tailoring the ratio of these functional units.The optimized block copolymer electrolyte has shown an amorphous crystalline structure,a high ionic conductivity of ~5.7×10^(-4)S cm^(-1),high lithium ion transference number(~0.49),wide electrochemical window up to ~4.65 V(vs.Li+/Li) and favorable mechanical strength at 55℃.Furthermore,the enhanced interface compatibility can well support the normal operations of lithium metal batteries using both LiFePO4 and LiNi0.8Co0.15Al0.05O2 cathodes.This study not only paves a new way to develop solid polymer electrolyte with optimizing functional units,but also provides a polymer electrolyte design strategy for the application demand of lithium metal battery.
基金supported by the Assistant Secretary for Energy Efficiency and Renewable Energy,Vehicle Technologies Office,under the Advanced Battery Materials Research(BMR)Program of the U.S.Department of Energy under Contract No.DE-AC02-05CH11231support by the U.S.Department of Energy under Contract No.106298-001+2 种基金the funding from Polish Ministry of Science and Higher Education No.1670/MOB/V/2017/0funding support of SUSTechthe resources of the National Energy Research Scientific Computing Center(NERSC)that is supported by the Office of Science of the U.S.Department of Energy。
文摘The lithium-sulfur(Li-S)battery is one of the most promising substitutes for current energy storage systems because of its low cost,high theoretical capacity,and high energy density.However,the high solubility of intermediate products(i.e.,lithium polysulfides)and the resultant shuttle effect lead to rapidly fading capacity and a low coulombic efficiency,which hinder the practical application of Li-S batteries.In this study,block copolymers are constructed with both an ethylene oxide unit and a styrene unit and then used as binders for Li-S batteries.Electrochemical performance improvements are attributed to the synergistic effects contributed by the different units of the block copolymer.The ethylene oxide unit traps polysulfide,which bonds strongly with the intermediate lithium polysulfide,and enhances the transport of lithium ions to reach high capacity.Meanwhile,the styrene unit maintains cathode integrity by improving the mechanical properties and elasticity of the constructed block copolymer to accommodate the large volume changes.By enabling multiple functions via different units in the polymer chain,high sulfur utilization is achieved,polysulfide diffusion is confined,and the shuttle effect is suppressed during the cycle life of Li-S batteries,as revealed by operando ultraviolet-visible spectroscopy and S Kedge X-ray absorption spectroscopy.
基金Project supported by the National Natural Science Foundation of China(Grant No.21373131)the Provincial Natural Science Foundation of Shanxi,China(Grant No.2015011004)the Research Foundation for Excellent Talents of Shanxi Provincial Department of Human Resources and Social Security,China
文摘We investigated phase transitions in a diblock copolymer–homopolymer hybrid system blended with nanorods(NRs)by using the time-dependent Ginzburg–Landau theory.We systematically studied the effects of the number,length and infiltration properties of the NRs on the self-assembly of the composites and the phase transitions occurring in the material.An analysis of the phase diagram was carried out to obtain the formation conditions of sea island structure nanorodbased aggregate,sea island structure nanorod-based dispersion,lamellar structure nanorod-based multilayer arrangement and nanowire structure.Further analysis of the evolution of the domain sizes and the distribution of the nanorod angle microphase structure was performed.Our simulation provides theoretical guidance for the preparation of ordered nanowire structures and a reference to improve the function of a polymer nanocomposite material.
基金Project supported by the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(Grant No.2019L0957)the Key Research and Development Project of the Introduction of High-Level Scientific and Technological Talents in Lvliang(Grant No.201701102)the Shanxi Provincial Natural Science Foundation,China(Grant No.201801D221109)。
文摘We investigate the microphase transition of asymmetric diblock copolymer induced by nanorods of different properties using cell dynamics simulation and Brown dynamics.The results show the phase diagram and representative nanostructures of the diblock copolymer nanocomposite.Various structures such as sea-island structure(SI),sea-island and lamellar structure(SI-L),and lamellar structure(L) are observed in the phase diagram.The system undergoes phase transition from SI-L to SI or from L to SI with increasing length of A-like sites for all numbers of nanorods except 10 and 300,and from SI to L with increasing number of nanorods for all lengths of A-like sites.Notably,the polymer system transforms from a tilted layered structure to a parallel lamellar,perpendicular lamellar,and subsequently sea-island structure with increasing length of A-like sites for a rod number of 240.To gain more detailed insight into these structural formation mechanisms,we analyze the evolution kinetics of the system with various lengths of A-like sites of the rods.The pattern evolution and domain growth of the ordered parallel/perpendicular lamellar structure are also investigated.Furthermore,the effects of the wetting strength,rod-rod interaction,polymerization degree,and length of nanorods on the self-assembled structure of asymmetric diblock copolymer/nanorods are studied.Our simulations provide theoretical guidance on the construction of complex-assembled structures and the design of novel functional materials.
