Design and application of MOFs and derived composite materials inlithium-sulfur batteries
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摘要: 在能源危机与环境问题日益凸显的背景下,电化学储能技术得到了迅速发展。在“超越锂”储能领域的竞争者中,锂硫电池(Li-S)因其具有高理论比容量、高质量能量密度并且环境友好、价格低廉等优点,成为最有前途的新储能技术。但是,锂硫电池的发展仍存在一些瓶颈问题需要解决,例如正极材料导电性能差、多硫化物穿梭效应及在充放电过程中电极体积膨胀等。作为锂硫电池的关键组成部分,电极和隔膜材料的设计和制备对解决这些问题及电池整体性能提升起到了重要的作用。金属有机骨架(MOFs)及衍生的复合材料作为锂硫电池电极或隔膜修饰材料,具有质量轻、电子和离子传导性好、孔道丰富和活性位点均匀分布等优势。此外,这类复合材料还具备形貌和组分可控、来源丰富和孔径可调等特性,从而便于机制研究。本文全面介绍了锂硫电池组成、工作原理并综述了近几年MOFs及衍生复合材料在锂硫电池中的研究进展,重点讨论了其在正极材料和隔膜材料中的应用,并对未来该材料在锂硫电池研究方向上的前景和突破进行了展望。Abstract: Against the background of increasingly prominent energy crisis and environmental problems, electrochemical energy storage technology has been developed rapidly. Among the competitors in the field of “beyond lithium” energy storage, lithium-sulfur batteries (Li-S) have become the most promising new energy storage technology owing to the advantages of high theoretical specific capacity, high mass energy density, environmental friendliness and low cost. However, there are still some bottleneck problems to be solved in the development of lithium-sulfur batteries, such as poor conductivity of cathode materials, polysulfide shuttle effect and electrode volume changes during charge and discharge. As the key components of lithium-sulfur batteries, the design and preparation of electrode and separator materials play the important roles in solving these problems and improving the overall performance of the batteries. Metal-organic frameworks (MOFs) and their derived composite materials exhibit the advantages of light weight, good electron and ion conductivity, abundant channels and uniform distribution of active sites to be used as electrode or separator modification materials for lithium-sulfur battery. In addition, this kind of composite material also possesses the characteristics of controllable morphology and composition, abundant source and adjustable pore size, which are convenient for mechanism research. Herein, we comprehensively introduce the composition, working mechanism and application of lithium-sulfur batteries. Importantly, we also review the research progress of MOFs and derivatives as cathode materials and separator materials in lithium-sulfur batteries in recent years. The prospects of the materials in improving the performance of lithium-sulfur batteries are also prospected.
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Key words:
- lithium-sulfur batteries /
- metal-organic frameworks /
- composite material /
- cathode /
- separator
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图 4 (a) S@氮掺杂碳(NC)/碳纳米管(CNT)复合材料制备过程示意图;(b) S@NC/CNT在0.5 C电流不同载硫量下的充放电性能;(c) S@NC/CNT在0.5 C电流下充放电曲线;(d) S@NC/CNT在1 C电流下充放电曲线;(e)不同电流下S@NC/CNT和S@NC的倍率性能比较[58]
Figure 4. (a) Schematic illustration of S@nitrogen doped carbon (NC)/carbon nanotube (CNT) preparation process; (b) Performance of S@NC/CNT cathode at different sulfur loading with the current rate of 0.5 C; (c) Charge-discharge profile of S@NC/CNT at the current rate of 0.5 C; (d) Cyclic performance of S@NC/CNT at 1 C; (e) Rate capability of S@NC/CNT and S@NC[58]
图 5 N-Co3O4@N-C的结构表征((a) SEM图像;(b) TEM图像;(c) HRTEM图像;(d) N2吸-脱附等温曲线;(e) XRD图谱;(f) EDS元素分布)[59]
Figure 5. Structure characterization of high sulfur carrier material N-Co3O4@N-C ((a) SEM image; (b) TEM image; (c) HRTEM image; (d) N2 adsorption-desorption isotherm curves; (e) XRD patterns; (f) EDS spectrum mapping)[59]
图 6 柔性MOF@PVDF-HFP隔膜((a)制备示意图;(b)光学照片;(c)俯视电镜图片及Cu、F元素分布;(d)侧视电镜图片;(e)放电过程中不同隔膜在可见H型Li-S电池中的光学图像)[68]
Figure 6. Flexible MOF@PVDF-HFP separator ((a) Schematic illustration; (b) Digital photos; (c) Top-view FE-SEM image with the corresponding elemental maps of Cu and F within the squared area; (d) Side-view FE-SEM image; (e) Optical images of visible H-type Li-S batteries with different separators during a discharging process)[68]
图 8 (a) NiCo2S4@C修饰的锂硫电池隔膜示意图;(b)传统Celgard隔膜表面SEM图像及插图对应光学照片;(c) NiCo2S4@C修饰的锂硫电池隔膜表面SEM图像及插图对应光学照片[73]
Figure 8. (a) Schematic configuration of Li-S battery with NiCo2S4@C-modified separator; (b) SEM image of traditional Celgard separator surface, and the inset corresponds to its optical photograph; (c) SEM image of NiCo2S4@C-modified separator surface, and the inset is its corresponding optical photograph[73]
图 9 (a) Co/mSiO2-NCNTs修饰的锂硫电池隔膜示意图;传统隔膜、(Co/NCNTs@mSiO2)/CNTs修饰隔膜和Co/mSiO2-NCNTs修饰隔膜电化学性能比较:(b)在0.1 C电流下的初始充放电曲线;(c)在0.1 C电流下循环性能;(d)不同电流密度下的倍率性能;(e) Co/mSiO2-NCNTs修饰隔膜在不同电流密度下的充放电曲线[76]
Figure 9. (a) Schematic illustration of Co/mSiO2-NCNTs-Coated Separator; Electrochemical properties of pristine separator, (Co/NCNTs@mSiO2)/CNTs-coated separator and Co/mSiO2-NCNTs-coated separator: (b) Initial discharge/charge curves at 0.1 C; (c) cycling performances at 0.1 C; (d) Rate performances at different current densities; (e) Discharge/charge curves of Co/mSiO2-NCNTs-coated separator at different current densities[76]
表 1 一些金属有机骨架(MOFs)及衍生复合材料作为锂硫电池正极材料的应用
Table 1. Application of some metal-organic frameworks (MOFs) and derivative composite materials as cathode for lithium-sulfur batteries
Sample MOFs Sulfur loading
percentage/%Reversible
capacity/(mA·h·g−1)Current
density/CCycle
numberVoltage vs.
Li/Li+/VRefs. MOFs as cathode MIL-100(Cr)/S@155 MIL-100(Cr) 48 — — — 1.0-3.0 49 S/ZIF-8 ZIF-8 30 710 1.0 300 1.8-2.8 50 Ni-MOF/S@155 Ni-MOF 82 689 0.1 100 1.5-3.0 51 NU-1000-AQ NU-1000 45 693 0.5 100 1.6-2.9 52 MOFs derived composite
materials as cathodeHPCN–S MOF-5 60 730 0.5 50 1.2-3.0 56 Co@N−C ZIF-67 93.6 1100 0.5 850 1.7-2.7 57 S-NPC/G ZIF-8/67 50 1025 0.1 300 1.7-2.8 58 S@NC/CNT ZIF-8/67 89 1141 0.5 120 1.5-2.8 53 N–Co3O4@N–C/rGO ZIF-67 — 611 2.0 1000 1.5-3.0 59 Mo2C–C NOs@S NENU-5 NOs 80 807 0.5 600 1.7-2.8 60 Fe3O4@C MIL-53 — 760 1.0 300 1.5-2.8 61 Cr2O3@C MIL-101(Cr) — 900 0.1 100 1.8-2.8 62 表 2 一些MOFs及衍生复合材料作为锂硫电池隔膜材料的应用
Table 2. Application of some MOFs and derivative composite materials as separator for lithium-sulfur batteries
Sample MOFs Reversible
capacity/(mA·h·g−1)Current
density/CCycle
numberVoltage vs.
Li/Li+/VRefs. MOFs as separator ZIF@T-PVDF ZIF-8 1 673 1 500 1.5-3.0 68 UiO-66-NH2@SiO2 UiO-66 910 0.1 100 1.6-3.0 69 Ce-MOF-2/CNT Ce-MOF 993.5 0.1 200 1.6-2.9 70 MIL-125(Ti)-modified PP/PE MIL-125(Ti) 612 2 200 1.7-2.7 71 ZIF-8@TBAC-PVDF ZIF-8 1324.2 2 700 1.5-3.0 72 MOFs derivative composite materials as separator NiCO2S4@C NieCo-PTA MOF 700 1 200 1.6-2.8 73 ZPC ZIF-8 907.1 0.1 50 1.5-3.0 74 Co9S8–Celgard ZIF-67 530 1 1000 1.8-2.8 75 ZIF-67@mSiO2 ZIF-67 552 5 250 1.5-3.0 76 -
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