有机-无机复合固态电解质在锂电池中的应用研究进展

Research Progress on Application of Organic-Inorganic Composite Solid Electrolyte in Lithium Batteries

高离子导电率、宽电化学窗口、高锂离子选择性和良好机械性能的固态电解质是高性能固态电池的核心。复合固态电解质具有良好的电化学性能和优异的机械性能,是目前固态电解质研究的主要方向之一。本综述总结了复合固态电解质的组成,锂离子的传输途径,重点阐述了每类复合固态电解质的制备、离子电导率和电池性能的研究进展;并探讨了复合固态电解质耐受锂金属还原性和高压正极氧化性的双层或多层结构设计。最后,概述了复合固态电解质面临的主要问题,指出高离子导电率和低界面阻抗的复合固态电解质仍是未来的主要研究内容。

Solid-state lithium-ion batteries(SSLBs)are one of the most promising next-generation batteries due to their excellent safety,higher energy density and longer cycle life.Solid-state electrolytes(SSEs)with a high ionic conductivity,a wide electrochemical window,and good mechanical properties are the importance of the high-performance SSLBs.The organic polymer SSEs have some advantages of flexibility and good mechanical property,that makes them almost have no serious interfacial problems.However,the low ionic conductivity is a major drawback for most polymer SSEs.Inorganic SSEs show a high ionic conductivity,a good electrochemical stability,and a high thermal stability,but their main disadvantages are a weak mechanical property(i.e.,brittle and fragile),a poor air stability and an inferior compatibility with metal lithium anode.Compared to inorganic and organic polymer SSEs,composite solid-state electrolytes(CSSEs)integrating the merits of organic polymers and inorganic electrolytes exhibit a good electrochemical performance and an excellent interface compatibility,which have attracted extensive attention in the SSEs research.This review detailly summarized the research progress on CSSEs in lithium batteries.The CSSEs are usually composed of inorganic fillers,organic polymers and lithium salts.The inorganic fillers are classified into inert and active fillers.The inert fillers,such as SiO_(2),Al_(2)O_(3) and TiO_(2),do not transport Li^(+)themselves,but can promote the ionic properties of polymer matrices.The active fillers conduct Li^(+)themselves including oxides(i.e.,perovskite-type,garnet-type,NASICON-type),sulfides,and halides,etc..Lithium salts used for the investigation of CSSEs include LiPF_6,LiBF_(4) and LiN(CF_(3)SO_(2))_(2)(LiTFSI),etc..The first CSSE with an inert filler was prepared via introducing an Al_(2)O_(3) into a matrix,thus improving the mechanical property of LiClO_(4)/PEO CSSEs at 100℃.SiO_(2) and TiO_(2) were a commonly used inert ceramic filler for the fabrication of CSSEs.The content,particle size and shape of metal oxide inert fillers affect the performance of CSSEs.The layered nano-sized claylike montmorillonite(MMT)as a passive filler was doped into polyvinylidene fluoride(PVDF)-hexafluoropropylene(HFP)polymer to prepare a ultraviolet(UV)-crosslinked MMT/PVDF-HFP membrane,having a room-temperature ionic conductivity of 1.6×10^(-3)S/cm.Carbon materials were also served as inert fillers to prepare CSSEs.The CSSEs with active fillers were synthesized via adding active fillers to polymers.Li_(0.5)La_(0.5)TiO_(3)(LLTO)is a typical perovskite-type active filler.The reduction of Ti ions in LLTO with lithium was prevented as combining LLZO with polymers,and the LLZO CSSEs exhibited a wide electrochemical window and a good stability.For instance,a PVDF polymer CSSEs with LLTO nanowires delivers a room temperature ion conductivity of 5.8×10^(-4)S/cm,an electrochemical window of 5.2 V,and a mechanical strength of 10 MPa.The cell of Li|PVDF/LLTO-15%/Li^(+)|LiFePO_(4)(LFP)has a superior Coulomb efficiency of approaching 100%after 200 cycles.The garnet-type active filler Li_(7)La_(3)Zr_(2)O_(12)(LLZO)and Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)were divided into zero-dimensional nanoparticles,one-dimensional nanowires and nanotubes,two-dimensional nanosheets,and three-dimensional structures according to the geometric structures.For instance,a LLZTO/PEO CSSEs was prepared by dispersing a zero-dimensional LLZTO powder into acetonitrile solution of PEO/LiTFSI.The room-temperature ion conductivity and electrochemical stability window of LLZTO/PEO CSSEs are 4.76×10^(-4)S/cm and 4.75 V,respectively.The multi-mixing CSSE membrane consisting of LLZTO,PEO,PVDF-HFP,and LiTFSI has a high ionic conductivity of 1.05×10^(-4)S/cm at 35℃,an electrochemical window of 5.2 V,and a high Li^(+)transference number of 0.52 at 60℃.A three-dimensional PVDF/LLZO/LiClO_(4) CSSEs was obtained by adding 3D coral-like LLZO nanofiller into PVDF/LiClO_(4).This CSSE membrane structured 3D interconnected framework has an enhanced ionic conductivity of 1.51×10^(-4)S/cm at room temperature.The assembled battery delivers a capacity retention of 95.2%after 200 cycles at1 C.The NASICON-type Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)and Li_(1.5)Al_(0.5)Ge_(1.5)(PO_(4))_(3)(LAGP)ceramics as active fillers were added into PEO and PVDF-HFP polymers.A PVDF-HFP/LiTFSI CSSE containing 50%(in mass fraction)LAGP displays the maximum ionic conductivity of 9.2×10^(-4)to 9.6×10^(-4)S/cm at room temperature.After 50 cycles,the cell with PVDF-HFP/50%LAGP/LiTFSI CSSE remains 141.3 mA?h/g and a capacity retention rate of 89.5%.Besides,sulfide fillers were investigated.However,sulfides are instability in air because it intrinsically tends to react with moisture to generate toxic H_(2)S gas.The CSSEs prepared with sulfide fillers improve asulfide stability and offer a high ion conductivity.For instance,adding sulfide active filler Li_(10)GeP_(2)S_(12)(LGPS)to PEO polymer can prepare a PEO/LGPS/LiTFSI CSSE membrane with a stability in air.The CSSE has an ionic conductivity of 1.18×10^(-4)S/cm at room temperature.After 150 cycles at0.5 C,the cells using PEO/LGPS/LiTFSI as a membrane demonstrates superior capacity retention and rate performance.To meet high-voltage cathodes and lithium metal,CSSEs with bi-layered or multi-layered structures maximize the synergistic effect of each layer without or withless sacrificing their properties,particularly for adjustable interphase.A bi-layer structure used Li_(6.4)La_(3)Zr_(2)Al_(0.2)O_(12)/PEO/LiTFSI and I_(2)/PEO/LiTFSI CSSE layers to contact with cathode and anode,respectively.After 500 cycles at0.2 C,the LFP||Li cell maintains a specific capacity of 146.20 mA?h/g.A sandwich structure CSSE with PAN/PVDF-80%(in mass)LLTO/PEO was prepared by a casting method,having an ionic conductivity of 2.81×10^(-4)S/cm and an electrochemical window of4.92 V.The assembled battery delivers the Coulomb efficiency of 99.2%and a capacity retention rate of 88%at 0.5 C after 500 cycles.The mechanism of ion transport in CSSEs has not yet clarified due to itscomplexity.The current well-known ion transport pathways in CSSEs include polymer matrix,inorganic active fillers and interfacial regions between polymer matrix and active fillers.Among them,the ion-transport pathway at the interfaces is relatively complex,and more efforts are needed to reveal the mechanism.Summary and prospects CSSEs have attracted great attention for the development of SSLBs because they can improve ionic conductivity and enhance the mechanical strength and stability of the SSEs by incorporating inorganic fillers into polymer electrolytes.Recent research progress on the CSSEs were summarized.The main components of the key materials of CSSEs,i.e.,inert and active fillers in the polymer matrix,were classified and summarized.The advanced structures of CSSEs to withstand lithium metal reduction and high-voltage positive electrode oxidation were explored.In addition,the possible mechanism of ion conductivity in CSSEs wasalso discussed.Although CSSEs were used in battery applications,they still had some challenges in ion conductivity,lithium-ion transport mechanism,and interface compatibility.Some key issues need to be considered for the future studies,i.e.,further increasing in the room-temperature ionic conductivity of CSSEs,understanding of ion conduction mechanism in different types of CSSEs,and optimizing the interphase between the solid electrolytes and the electrodes.