随着现代社会的发展，能源的需求也日益增长，其不可再生性和与日俱增的需求有着不可调和的矛盾。因此，开发高效储能元件成为解决这个问题的主要方式。在目前的主流储能技术中，电化学储能因其灵活性和高效性得到广泛应用，尤其是电池技术已经成为重要的电化学储能形式。锂离子电池（LIBs）具有能量密度高、循环寿命长和环境友好等特点，设计适于储锂电极材料对于提高LIBs性能十分重要。金属有机框架材料（MOFs），是一种由有机配体和金属离子或团簇通过配位键自组装而成的一类具有分子内孔隙的有机-无机杂化材料，具有丰富的活性位点、灵活的孔隙和独特的氧化还原性，在锂离子电池电极材料中有较大的应用潜力。

基于此，本文合成了一种四氮杂冠醚有机配体，即11,23-二甲基-3,7,15,19-四氮杂-三环[19,13,1,19,13]二十六-1(25),9,11,13(26),21,23-己烯-25,26-二醇(L)，并选取过渡金属、无机酸或多金属氧酸盐为无机构件，利用溶剂热法成功合成出三种新型氮杂冠醚基金属有机框架材料：[Cu₂(L)(H₂O)₂](HPO₄)₂ (MOF-1)、[Ni₂(L)](Mo₂O₇) (MOF-2)和[Ni₅(L)_2.5(H₂O)₅](PNiW₁₁O₃₉)·2H₂O (MOF-3)。利用单晶X-射线衍射（SCXRD）、X-射线粉末衍射（PXRD）、傅里叶红外光谱（FT-IR）、热重分析（TGA）、扫描电子显微镜（SEM）和X-射线光电子能谱（XPS）对材料的结构及锂化性质进行了表征。三种晶体材料均具有电化学活性，为了提升材料的电化学储能性能和导电性，通过湿浸法引入SnO₂制备了相应的复合材料（SnO₂@MOF-n，n = 1-3），并详细研究了复合材料的电化学储能性能与机理。主要研究内容与结果如下：

单晶X-射线衍射数据表明，MOF-1的Cu(II)金属中心与配体L、磷酸氢根阴离子和水分子相连形成六配位八面体构型，呈零维结构。MOF-2的Ni(II)金属中心与配体中的N、O相连形成变形八面体构型，配体L-Ni单元间通过[Mo₂O₇]^2-阴离子团簇桥连形成一维链状结构。MOF-3的金属中心Ni(II)与配体中的N、O原子呈螯合配位模式，磷钨酸中的一个W被过渡金属Ni取代形成过渡金属杂多酸[PNiW₁₁O₃₉]^5-，并与金属中心相连形成零维结构。通过PXRD、IR和TGA分析了MOFs-1-3及其复合材料的理化性质，结果表明，三种晶体材料纯度较高并且复合成功，且具有较好的热稳定性。电化学性能测试结果表明，MOFs-1-3材料的可逆比容量分别为53.1、216.9以及353.2 mA h g^-1，说明不同阴离子与过渡金属构建的MOFs材料，在电化学储能性能方面存在较大差异。为提升晶体材料的电化学性能，采用湿浸法引入SnO₂制备MOFs-1-3的复合材料SnO₂@MOFs-1-3，其可逆比容量分别提升至643、754.6以及771 mA h g^-1。通过XPS和SEM对于MOFs-1-3及其复合材料SnO₂@MOFs-1-3循环前后的形貌特征以及价态变化进行分析，探究了其可能的储锂机理。研究结果表明，SnO₂@MOFs-1-3复合材料的储能机理与过渡金属离子（Cu，Ni）、多金属氧酸盐（Mo，W）、富氮有机配体和SnO₂可逆转化的协同作用有关。

With the development of modern society, the demand for energy continues to grow, which leads to an irreconcilable contradiction between its non-renewable nature and the ever-increasing needs. Therefore, developing high-efficiency energy storage components has become a primary solution to this issue. Among current mainstream energy storage technologies, electrochemical energy storage is widely adopted due to its flexibility and high efficiency with battery technology, emerging as a crucial form of electrochemical energy storage. Lithium-ion batteries (LIBs) are characterized by high energy density, long cycle life, and environmental friendliness, making the design of suitable lithium storage electrode materials essential for enhancing LIB performance. Metal-organic frameworks (MOFs), as a class of organic-inorganic hybrid materials with intrinsic porosity formed through the self-assembly of organic ligands and metal ions or clusters via coordination bonds, exhibit abundant active sites, tunable pores, and unique redox properties. These features grant them significant potential for application in lithium-ion battery electrode materials.

Based on this, this study synthesized a nitrogen-containing crown ether organic ligand, namely 11,23-dimethyl-3,7,15,19-tetraaza-tricyclo[19,13,1,19,13]hexacosa-1(25),9,11,13(26),21,23-hexaene-25,26-diol (L). Using transition metals, inorganic acids, or polyoxometalates as inorganic building blocks, three novel nitrogen-containing crown ether-based metal-organic frameworks (MOFs) have been successfully synthesized via a solvothermal method, which were [Cu₂(L)(H₂O)₂](HPO₄)₂ (MOF-1), [Ni₂(L)](Mo₂O₇) (MOF-2), and [Ni₅(L)_2.5(H₂O)₅](PNiW₁₁O₃₉)·2H₂O (MOF-3).The structures and lithiation properties of these materials were characterized using single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Given the electrochemical activity of these three crystalline materials, to enhance their electrochemical energy storage performance and conductivity, SnO₂ was introduced via a wet impregnation method to prepare corresponding composite materials (SnO₂@MOF-n, n = 1-3). The electrochemical energy storage performance and mechanisms of these composites were thoroughly investigated. The main research contents and results are as follows:

Single-crystal X-ray diffraction data reveal that in MOF-1, the Cu (II) metal center is coordinated with ligand L, hydrogen phosphate anions, and water molecules, forming a six-coordinated octahedral configuration, resulting in a zero-dimensional structure. In MOF-2, the Ni(II) metal center is connected to N and O atoms of the ligand, forming a distorted octahedral configuration. The L-Ni units are bridged by [Mo₂O₇]^2- anion clusters to form a one-dimensional chain structure. In MOF-3, the Ni (II) metal center chelates with N and O atoms of the ligand, while one W atom in the phosphotungstic acid is substituted by the transition metal Ni, forming a transition metal-substituted heteropolyacid [PNiW₁₁O₃₉]^5-, which connects with the metal center to form a zero-dimensional structure. The physicochemical properties of MOFs-1-3 and their composites were analyzed by PXRD, IR, and TGA. The results indicate that the three crystalline materials are of high purity, successfully composited, and exhibit good thermal stability. Electrochemical performance tests show that the reversible specific capacities of MOFs-1-3 are 53.1, 216.9, and 353.2 mA h g^-1, respectively, suggesting significant differences in electrochemical energy storage performance due to the different anions and transition metals used in their construction. To enhance the electrochemical performance of the crystalline materials, SnO₂ was introduced via a wet impregnation method to prepare SnO₂@MOFs-1-3 composites. Their reversible specific capacities increased to 643, 754.6, and 771 mA h g^-1, respectively. XPS and SEM were employed to analyze the morphological features and valence state changes of MOFs-1-3 and their composites SnO₂@MOFs-1-3 before and after cycling, revealing their lithium storage mechanisms. The results demonstrate that the energy storage mechanism of the SnO₂@MOFs-1-3 composite materials is associated with the synergistic effects of transition metal ions (Cu, Ni), polyoxometalates (Mo, W), nitrogen-rich organic ligands, and the reversible conversion of SnO₂

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