以阳离子型MOF-867-Me作为填料,与PEO、[(氰基)(4-氟苯磺酰基)]亚胺锂(LiFBCSI)共混,通过溶液浇铸法制备了复合聚合物电解质隔膜(CPE),采用红外光谱(FT-IR)、X射线衍射(XRD)、扫描电镜(SEM)、差示量热(DSC)和电化学阻抗谱(EIS)等手段对样品进行表征,研究了电解质隔膜的离子导电性,并将隔膜用于磷酸铁锂电池中。结果表明:当MOF-867-Me添加量为10%时,复合聚合物电解质隔膜PEO16/LiFBCSI/MOF-867-Me(10%)在60℃下离子电导率达到2.43×10-4S/cm,锂离子迁移数从未添加的0.24提高到0.56。MOF-867-Me表面呈正电,有利于锂盐解离,增强了电解质的导电能力。组装的LiFePO4/CPE/Li电池的首次放电比容量达到159.8mAh/g,循环45圈后放电比容量仍有150.8mAh/g,容量保持率为94%,表现出较为优异的应用前景。
Composite polymer electrolytes (CPE) were prepared by solution casting method using cationic MOF-867-Me as a filler,blended with PEO and lithium [(cyano) (4-fluorobenzenesulfonyl)] imide (LiFBCSI).The samples were characterized by FT-IR,XRD,SEM,DSC,and EIS,and the ionic conductivity of the electrolyte separator was studied.The separator was subsequently utilized in LiFePO4 batteries.The results showed that the ionic conductivity of the composite polymer electrolyte separator PEO16/LiFBCSI/MOF-867-Me(10%) reached 2.43×10-4S/cm at 60℃,and the lithium-ion transference number increased from 0.24 without the addition of MOF-867-Me to 0.56.The surface of MOF-867-Me was positively charged,which facilitated the dissociation of lithium salts and improved the conductivity of the electrolyte.The initial discharge specific capacity of the assembled LiFePO4/CPE/Li battery reached 159.8mAh/g,and remained 150.8mAh/g after 45 cycles,with a capacity retention rate of 94%,demonstrating promising application prospects.
[1] Zeng G,Zhao J,Feng C,et al.Flame-retardant bilayer separator with multifaceted van der waals interaction for lithium-ion batteries[J].ACS Applied Materials & Interfaces,2019,11(29):26402-26411.
[2] Wang Q,Jiang L,Yu Y,et al.Progress of enhancing the safety of lithium ion battery from the electrolyte aspect[J].Nano Energy,2019,55:93-114.
[3] Wang G,He P,Fan L-Z.Asymmetric polymer electrolyte constructed by metal-organic framework for solid-state,dendrite-free lithium metal battery[J].Advanced Functional Materials,2021,31(3):2007198.
[4] Zha W,Chen F,Yang D,et al.High-performance Li6.4La3Zr1.4Ta0.6O12/Poly(ethylene oxide)/succinonitrile composite electrolyte for solid-state lithium batteries[J].Journal of Power Sources,2018,397:87-94.
[5] Blake A J,Kohlmeyer R R,Hardin J O,et al.3D Printable ceramic-polymer electrolytes for flexible high-performance Li-ion batteries with enhanced thermal stability[J].Advanced Energy Materials,2017,7(14):1602920.
[6] 付茹,王子阳,邹海凤,等.导电聚合物电解质隔膜PEO/LiPCSI的制备及性能研究[J].化工新型材料,2024,52(7):143-147,156.
[7] Zhou D,Shanmukaraj D,Tkacheva A,et al.Polymer electrolytes for lithium-based batteries:advances and prospects[J].Chem,2019,5(9):2326-2352.
[8] Lu Y,Zeng X,Wang J,et al.Ultrathin LiV2O4 layers modified LiNi0.5Co0.2Mn0.3O2 single-crystal cathodes with enhanced activity and stability[J].Advanced Materials Interfaces,2019,6(22):1901368.
[9] Sheng O,Jin C,Luo J,et al.Mg2B2O5 Nanowire enabled multifunctional solid-state electrolytes with high ionic conductivity,excellent mechanical properties,and flame-retardant performance[J].Nano Letters,2018,18(5):3104-3112.
[10] Ban X,Zhang W,Chen N,et al.A high-performance and durable poly(ethylene oxide)-based composite solid electrolyte for all solid-state lithium battery[J].Journal of Physical Chemistry C,2018,122(18):9852-9858.
[11] Yang X Y,Wei T,Li J S,et al.Polyoxometalate-incorporated metallapillararene/metallacalixarene metal-organic frameworks as nodae materials for lithium ion batteries[J].Inorganic Chemistry,2017,56(14):8311-8318.
[12] Lu J,Wang Z,Zhang Q,et al.The effects of amino groups and open metal sites of MOFs on polymer-based electrolytes for all-solid-state lithium metal batteries[J].Chinese Journal of Chemical Engineering,2023,60:80-89.
[13] Sun C C,Yusuf A,Li S W,et al.Metal organic frameworks enabled rational design of multifunctional PEO-based solid polymer electrolytes[J].Chemical Engineering Journal,2021,414:128702.
[14] Han Q,Wang S,Jiang Z,et al.Composite polymer electrolyte incorporating metal-organic framework nanosheets with improved electrochemical stability for all-solid-state Li metal batteries[J].ACS Applied Materials & Interfaces,2020,12(18):20514-20521.
[15] Lu X,Wu H,Kong D,et al.Facilitating lithium-ion conduction in gel polymer electrolyte by metal-organic frameworks[J].ACS Materials Letters,2020,2(11):1435-1441.
[16] Yuan H,Luan J,Yang Z,et al.Single lithium-ion conducting solid polymer electrolyte with superior electrochemical stability and interfacial compatibility for solid-state lithium metal batteries[J].ACS Applied Materials & Interfaces,2020,12(6):7249-7256.
[17] Choi K M,Jeong H M,Park J H,et al.Supercapacitors of nanocrystalline metal-organic frameworks[J].ACS Nano,2014,8(7):7451-7457.
[18] Xu L,Luo Y,Sun L,et al.Tuning the properties of the metal-organic framework UiO-67-bpy via post-synthetic N-quaternization of pyridine sites[J].Dalton Transactions,2016,45(20):8614-8621.
[19] Huo H,Wu B,Zhang T,et al.Anion-immobilized polymer electrolyte achieved by cationic metal-organic framework filler for dendrite-free solid-state batteries[J].Energy Storage Materials,2019,18:59-67.
[20] Ma Y,Matsuda R,Sato H,et al.A convenient strategy for designing a soft nanospace:an atomic exchange in a ligand with isostructural frameworks[J].Journal of the American Chemical Society,2015,137(50):15825-15832.
[21] Ji H,Naveen K,Lee W,et al.Pyridinium-functionalized ionic metal-organic frameworks designed as bifunctional catalysts for CO2 fixation into cyclic carbonates[J].ACS Applied Materials & Interfaces,2020,12(22):24868-24876.
[22] Velthoen M E Z,Nab S,Weckhuysen B M.Probing acid sites in solid catalysts with pyridine UV-Vis spectroscopy[J].Physical Chemistry Chemical Physics,2018,20(33):21647-21659.
基金资助
国家自然科学基金(22062004);贵州师范大学学术新苗基金(黔师新苗[2021]A08号)
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