离子液体非共价诱导制备碳纳米管/石墨烯集流体用于钠金属负极

doi:10.6023/A23050220

摘要/Abstract

钠金属电池因丰富的钠资源储备在大规模储能中具有广泛的应用前景. 然而钠金属电池存在钠金属活性高、形成的固体电解质界面膜(SEI膜)不稳定、金属钠体积膨胀大等问题, 限制了其应用. 本工作利用离子液体与sp²碳间的非共价作用, 诱导碳纳米管和还原氧化石墨烯进行自组装, 制备得到了碳纳米管支撑的石墨烯高导电三维多孔碳(3D-GC)集流体. 制备得到的3D-GC具有三维多孔结构, 可以为金属钠提供较大的储存空间. 另外, 复合材料具有较高的导电性, 得到了较低的金属钠的沉积过电位(5.6 mV). 3D-GC@Na负极具有良好的电化学性能, 在电流密度为1 mA•cm⁻², 沉积容量为1 mAh•cm⁻²时, 在240次充放电循环过程中始终保持了较高的库伦效率(CE), 平均CE为99.6%. 与Na₃V₂(PO₄)₂F₃组装全电池也表现出优异的电化学性能.

关键词: 离子液体, 还原氧化石墨烯, 碳纳米管, 非共价作用, 钠金属负极

Sodium metal batteries have been regarded as promising candidates for next-generation energy storage systems due to their impressive capacity and natural abundance. However, the high reactivity of Na, unstable solid electrolyte interface (SEI) and Na metal dendrite growth with safety hazards inhibit their applications. Various strategies have been proposed to solve the above issues. Designing porous current collectors has been recognized as one of the most promising solutions. Porous carbon/carbon nanotubes/graphene- based materials are widely investigated as host materials for sodium metal anode. However, the sp² carbon faces serious issues, such as aggregation or stacking because of their π-π interactions. Herein, we tackle this issue by using ionic liquid as additive during hydrothermal process. The non-covalent interaction between 1-butyl-3-methylimidazolium (Bmim⁺) and sp² carbon (carbon nanotubes and reduced graphene oxide) helps to inhibit the aggregation of CNTs and the stacking of rGO layers. Also, their interactions induced the CNTs and rGO to form three dimensional (3D) porous carbon (3D-GC) current collector. The ionic liquid 1-butyl-3-methylimidazolium bisulfate ([Bmim][HSO₄]) plays great role as a stabilizer and surfactant. The reduced surface tension of the system is also favorable for uniformly interweaving the CNTs and rGO. The prepared 3D-GC exhibit micro-meso-macro porous structure, which provides a large storage space for sodium metal. Meantime, the composite shows a high electrical conductivity, leading to a low deposition overpotential (5.6 mV) of sodium metal. As a result, the 3D-GC@Na anode exhibit an impressive cycling stability for over 1450 cycles (2900 h) at 1 mA•cm⁻² with a capacity of 1 mAh•cm⁻². Moreover, when being used in full cells with Na₃V₂(PO₄)₂F₃ as cathode, they also show well performances.

Key words: ionic liquid, reduced graphene oxide, carbon nanotube, non-covalent interaction, sodium metal anode

引用此文

刘稳, 王昱捷, 杨慧琴, 李成杰, 吴娜, 颜洋. 离子液体非共价诱导制备碳纳米管/石墨烯集流体用于钠金属负极[J]. 化学学报, 2023, 81(10): 1379-1386.

Wen Liu, Yujie Wang, Huiqin Yang, Chengjie Li, Na Wu, Yang Yan. The Preparation of Carbon Nanotubes/Reduced Graphene Oxide Current Collector by Non-covalent Induction of Ionic Liquid for Sodium Metal Anode[J]. Acta Chimica Sinica, 2023, 81(10): 1379-1386.

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图/表 5

图1. (a) rGO, (b) GC和(c) 3D-GC的SEM图; (d) GC和(e) 3D-GC的TEM图; 三种材料的(f)电子电导率, (g) N2等温吸-脱附曲线, (h)孔径分布和(i)塔菲尔曲线图(0.01 V?s?1)

Figure 1. SEM images of (a) rGO, (b) GC and (c) 3D-GC; TEM images of (d) GC and (e) 3D-GC; (f) electronic conductivity, (g) N2 adsorption- desorption isotherms, (h) pore size distribution and (i) Tafel plots of rGO, GC and 3D-GC (0.01 V?s?1)

图2. (a)和(d) rGO, (b)和(e) GC, (c)和(f) 3D-GC电极在0.5 mA?cm?2电流密度和不同容量下进行镀钠的SEM图; (g) 3D-GC在0.5 mA?cm?2电流密度和2 mAh?cm?2容量下镀钠的截面SEM图; (h~l) 镀Na的3D-GC的EDX元素图, (m) rGO、GC和3D-GC沉积曲线

Figure 2. SEM images of (a) and (d) rGO, (b) and (e) GC, (c) and (f) 3D-GC electrodes at 0.5 mA?cm?2 with different capacities; (g) cross-section SEM image of the 3D-GC electrodes at 0.5 mA?cm?2 with a capacity of 2 mAh?cm?2; (h~l) EDX elemental mapping images of Na-plated in 3D-GC; (m) nucleation overpotentials of Na plating with rGO, GC and 3D-GC as current collector

图3. GO, GC和3D-GC在(a) 0.5 mA?cm?2下的库伦效率图; (b) 0.5 mA?cm?2下, 不同圈数的电压-容量曲线; (c)在1 mA?cm?2下的库伦效率图; (d) 1 mA?cm?2下, 不同循环圈数的电压-容量曲线; (e)在不同电流密度下的倍率性能图

Figure 3. (a) Coulombic efficiency profiles of rGO, GC and 3D-GC at 0.5 mA?cm?2; (b) voltage-capacity profiles after different cycles at 0.5 mA?cm?2; (c) Coulombic efficiency profiles of rGO, GC and 3D-GC at 1 mA?cm?2; (d) voltage-capacity profiles after different cycles at 1 mA?cm?2; (e) rate capability of rGO, GC and 3D-GC at different current densities

图4. 以rGO、GC和3D-GC为基底的对称电池在不同电流密度、沉积容量为1 mAh?cm?2的循环性能图及局部放大图: (a) 0.5 mA?cm?2 (b) 1 mA?cm?2; (c) 以rGO, GC和3D-GC为基底的对称电池在不同电流密度下沉积容量为1 mAh?cm?2的倍率性能图; 对称电池在不同电流密度下的电压与容量曲线: (d) GC, (e) 3D-GC

Figure 4. Cycling performance comparisons of rGO, GC and 3D-GC symmetrical cells with a limited capacity of 1 mAh?cm?2 and local enlarged view: (a) 0.5 mA?cm?2, (b) 1 mA?cm?2; (c) rate performance plot of sodium-symmetric cells based on rGO, GC and 3D-GC with a deposition capacity of 1 mAh?cm?2 at different current densities; voltage-capacity curves of symmetrical cells at different current densities: (d) GC, (e) 3D-GC

图5. (a) GC@Na//Na3V2(PO4)2F3、rGO@Na//Na3V2(PO4)2F3和3D-GC@Na//Na3V2(PO4)2F3倍率性能图; (b) 3D-GC@Na//Na3V2(PO4)2F3和(d) GC@Na//Na3V2(PO4)2F3的充放电曲线图; (c) 3D-GC@Na//Na3V2(PO4)2F3的CV图; (e) GC@Na//Na3V2(PO4)2F3和3D-GC@Na//Na3V2(PO4)2F3循环性能图

Figure 5. (a) Rate capabilities of GC@Na//Na3V2(PO4)2F3, rGO@Na//Na3V2(PO4)2F3 and 3D-GC@Na//Na3V2(PO4)2F3; charge-discharge curves of (b) 3D-GC@Na//Na3V2(PO4)2F3 and (d) GC@Na//Na3V2(PO4)2F3; (c) CV curve of 3D-GC@Na//Na3V2(PO4)2F3; (e) the cycling performances of GC@Na//Na3V2(PO4)2F3 and 3D-GC@Na//Na3V2(PO4)2F3

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