摘要
Sulfide solid electrolytes are promising for high energy density and safety in all-solid-state batteries due to their high ionic conductivity and good mechanical properties.However,the application of sulfide solid electrolytes in all-solid-state batteries with lithium anode is restricted by the side reactions at lithium/electrolytes interfaces and the growth of lithium dendrite caused by nonuniform lithium deposition.Herein,a homogeneous LiF-Li_(3)N composite protective layer is in situ formed via a manipulated reaction of pentafluorobenzamide with Li metal.The LiF-Li_(3)N layer with both high interfacial energy and interfacial adhesion energy can synergistically suppress side reactions and inhibit the growth of lithium dendrite,achieving uniform deposition of lithium.The critical current densities of Li_(10)GeP_(2)S_(12)and Li_(6)PS_(5)Cl are increased to 3.25 and 1.25 mA cm^(-2)with Li@LiF-Li_(3)N layer,which are almost triple and twice as those of Li-symmetric cells in the absence of protection layer,respectively.Moreover,the Li@LiF-Li_(3)N/Li10GeP2S12/Li@LiF-Li_(3)N cell can stably cycle for 9000 h at 0.1 mA cm^(-2)under 0.1 mA h cm^(-2),and Li@LiF-Li_(3)N/Li_(6)PS_(5)Cl/Li@LiF-Li_(3)N cell achieves stable Li plating/stripping for 8000 h at 0.1 mA cm^(-2)under10 m A h cm^(-2).The improved dynamic stability of lithium plating/stripping in Li@LiF-Li_(3)N/Li_(10)GeP_(2)S_(12)or Li_(6)PS_(5)Cl interfaces is proved by three-electrode cells.As a result,LiCoO_(2)/electrolytes/Li@LiF-Li_(3)N batteries with Li_(10)GeP_(2)S_(12)and Li_(6)PS_(5)Cl exhibit remarkable cycling stability of 500 cycles with capacity retentions of 93.5%and 89.2%at 1 C,respectively.
基金
supported by the National Key R&D Program of China(2022YFB3807700)
the National Natural Science Foundation of China(U1964205,51872303,52172253)
the Ningbo S&T Innovation 2025 Major Special Programme(2019B10044,2021Z122)
the Zhejiang Provincial Key R&D Program of China(2022C01072)
the Jiangsu Provincial S&T Innovation Special Programme for carbon peak and carbon neutrality(BE2022007)
the Youth Innovation Promotion Association CAS(Y2021080)。