Polymer-based composite electrolytes composed of three-dimensional Li_(6.4)La_(3)Zr_(2)Al_(0.2)O_(12)(3D-LLZAO)have attracted increasing attention due to their continuous ion conduction and satisfactory mechanical pro...Polymer-based composite electrolytes composed of three-dimensional Li_(6.4)La_(3)Zr_(2)Al_(0.2)O_(12)(3D-LLZAO)have attracted increasing attention due to their continuous ion conduction and satisfactory mechanical properties.However,the organic/inorganic interface is incompatible,resulting in slow lithium-ion transport at the interface.Therefore,the compatibility of organic/inorganic interface is an urgent problem to be solved.Inspired by the concept of“gecko eaves”,polymer-based composite solid electrolytes with dense interface structures were designed.The bridging of organic/inorganic interfaces was established by introducing silane coupling agent(3-chloropropyl)trimethoxysilane(CTMS)into the PEO-3D-LLZAO(PL)electrolyte.The in-situ coupling reaction improves the interface affinity,strengthens the organic/inorganic interaction,reduces the interface resistance,and thus achieves an efficient interface ion transport network.The prepared PEO-3D-LLZAO-CTMS(PLC)electrolyte exhibits enhanced ionic conductivity of 6.04×10^(-4)S cm^(-1)and high ion migration number(0.61)at 60℃and broadens the electrochemical window(5.1 V).At the same time,the PLC electrolyte has good thermal stability and high mechanical properties.Moreover,the Li Fe PO_(4)|PLC|Li battery has excellent rate performance and cycling stability with a capacity decay rate of 2.2%after 100 cycles at 60℃and 0.1 C.These advantages of PLC membranes indicate that this design approach is indeed practical,and the in-situ coupling method provides a new approach to address interface compatibility issues.展开更多
The development of lithium-sulfur(Li-S) battery as one of the most attractive energy storage systems among lithium metal batteries is seriously hindered by low sulfur utilization, poor cycle stability and uneven redep...The development of lithium-sulfur(Li-S) battery as one of the most attractive energy storage systems among lithium metal batteries is seriously hindered by low sulfur utilization, poor cycle stability and uneven redeposition of Li anode. It is necessary to propose strategies to address the problems as well as improve the electrochemical performance. One of the effective solutions is to improve the sulfiphilicity of sulfur cathode and the lithiophilicity of the Li anode. Herein, we reported that a synergistic functional separator(graphene quantum dots(GQDs)-polyacrylonitrile(PAN) @polypropylene(PP) separator)improved the electrochemical activity of sulfur cathode as well as the stability of Li anode. GQDs induced uniform Li^(+)nucleation and deposition, which slowed down the passivation of Li anode and avoided shortcircuit. Further, three-dimensional network constructed by electrospinning nanofibers and the polar functional groups of GQDs could both effectively inhibit the shuttle of LiPSs and improve the sulfur utilization. The stability of Li-S battery was improved by the synergistic effect. In addition, GQDs and electrospinning nanofibers protector increased lifetime of separators. Benefiting from the unique design strategy, Li//Li symmetric battery with GQDs-PAN@PP separators exhibited stably cycling for over 600 h. More importantly, the Li-S full batteries based GQDs-PAN@PP separators enabled high stability and desirable sulfur electrochemistry, including high reversibility of 558.09 mA h g^(-1)for 200 cycles and durable life with a low fading rate of 0.075% per cycle after 500 cycles at 0.5 C. Moreover, an impressive areal capacity of 3.23 mA h cm^(-2)was maintained under high sulfur loading of 5.10 mg cm^(-2). This work provides a new insight for modification separator to improve the electrochemical performance of Li-S/Li metal batteries.展开更多
基金supported by the Key Program(U20A20235)funded by the National Natural Science Foundation of Chinathe National Natural Science Foundation of China(52171127,51974242)+3 种基金the Natural Science Basic Research Program of Shaanxi(2023-JC-QN-0595)the Regional Innovation Capability Guidance Program of Shaanxi(2022QFY10-06)the Key R&D Program of Xianyang Science and Technology Bureau(2021ZDYF-GY-0029)the Program of Xi’an Science and Technology Bureau(23GXFW0066)。
文摘Polymer-based composite electrolytes composed of three-dimensional Li_(6.4)La_(3)Zr_(2)Al_(0.2)O_(12)(3D-LLZAO)have attracted increasing attention due to their continuous ion conduction and satisfactory mechanical properties.However,the organic/inorganic interface is incompatible,resulting in slow lithium-ion transport at the interface.Therefore,the compatibility of organic/inorganic interface is an urgent problem to be solved.Inspired by the concept of“gecko eaves”,polymer-based composite solid electrolytes with dense interface structures were designed.The bridging of organic/inorganic interfaces was established by introducing silane coupling agent(3-chloropropyl)trimethoxysilane(CTMS)into the PEO-3D-LLZAO(PL)electrolyte.The in-situ coupling reaction improves the interface affinity,strengthens the organic/inorganic interaction,reduces the interface resistance,and thus achieves an efficient interface ion transport network.The prepared PEO-3D-LLZAO-CTMS(PLC)electrolyte exhibits enhanced ionic conductivity of 6.04×10^(-4)S cm^(-1)and high ion migration number(0.61)at 60℃and broadens the electrochemical window(5.1 V).At the same time,the PLC electrolyte has good thermal stability and high mechanical properties.Moreover,the Li Fe PO_(4)|PLC|Li battery has excellent rate performance and cycling stability with a capacity decay rate of 2.2%after 100 cycles at 60℃and 0.1 C.These advantages of PLC membranes indicate that this design approach is indeed practical,and the in-situ coupling method provides a new approach to address interface compatibility issues.
基金supported by Key Program (U20A20235) funded by National Natural Science Foundation of Chinathe National Natural Science Foundation of China (52171127, 51974242)+2 种基金Regional Innovation Capability Guidance Program of Shaanxi Provincial Government (2022QFY10-06)Key R&D Program of Xianyang Science and Technology Bureau (2021ZDYF-GY-0029)Doctoral dissertation innovation fund (310-252072201) by Xi’an University of Technology。
文摘The development of lithium-sulfur(Li-S) battery as one of the most attractive energy storage systems among lithium metal batteries is seriously hindered by low sulfur utilization, poor cycle stability and uneven redeposition of Li anode. It is necessary to propose strategies to address the problems as well as improve the electrochemical performance. One of the effective solutions is to improve the sulfiphilicity of sulfur cathode and the lithiophilicity of the Li anode. Herein, we reported that a synergistic functional separator(graphene quantum dots(GQDs)-polyacrylonitrile(PAN) @polypropylene(PP) separator)improved the electrochemical activity of sulfur cathode as well as the stability of Li anode. GQDs induced uniform Li^(+)nucleation and deposition, which slowed down the passivation of Li anode and avoided shortcircuit. Further, three-dimensional network constructed by electrospinning nanofibers and the polar functional groups of GQDs could both effectively inhibit the shuttle of LiPSs and improve the sulfur utilization. The stability of Li-S battery was improved by the synergistic effect. In addition, GQDs and electrospinning nanofibers protector increased lifetime of separators. Benefiting from the unique design strategy, Li//Li symmetric battery with GQDs-PAN@PP separators exhibited stably cycling for over 600 h. More importantly, the Li-S full batteries based GQDs-PAN@PP separators enabled high stability and desirable sulfur electrochemistry, including high reversibility of 558.09 mA h g^(-1)for 200 cycles and durable life with a low fading rate of 0.075% per cycle after 500 cycles at 0.5 C. Moreover, an impressive areal capacity of 3.23 mA h cm^(-2)was maintained under high sulfur loading of 5.10 mg cm^(-2). This work provides a new insight for modification separator to improve the electrochemical performance of Li-S/Li metal batteries.
