Zhou Fang, Li Shuangfu, Han Kai, Li Yajuan, Liu You-Nian
Hunan Provincial Key Laboratory of Efficient and Clean Utilization of Manganese Resources, College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, Hunan, China.
Dalton Trans. 2021 Jan 19;50(2):535-545. doi: 10.1039/d0dt03540h.
Manganese-based transition metal oxides are regarded as one kind of high capacity and low cost anode material for Li-ion batteries. To overcome the challenges of poor electrical conductivity and large volumetric expansion during the charging-discharging process of MnO, we here synthesize MnO@carbon (MnO@C) nanowires via the polymerization inspired in situ growth of [Mn-NTA] (NTA = nitrilotriacetic acid) precursor nanowires with a subsequent heat treatment process. The growth mechanism of [Mn-NTA] precursor nanowires was studied. The morphology of the precursor nanowires depended largely on the molar ratio of MnCl2 to NTA reactants. At a molar ratio of 2, the length of the [Mn-NTA] nanowires reached up to more than 140 μm. Furthermore, the as-synthesized MnO@C nanowires were integrated with a very low content of reduced graphene oxide (rGO) to prepare a self-standing paper-like MnO@C/rGO anode for lithium ion batteries without a binder. The MnO@C/rGO anode showed a unique structure with one-dimensional porous MnO nanowires hierarchically encapsulated by a conductive carbon framework. As a result, the self-standing electrode achieved a high capacity of 1368 mA h g-1 after 100 cycles at a current density of 100 mA g-1 and prominent cycling stability with a capacity of 689.9 mA h g-1 even after 1700 cycles at 2000 mA g-1.
锰基过渡金属氧化物被视为锂离子电池的一种高容量、低成本负极材料。为了克服MnO在充放电过程中电导率差和体积膨胀大的挑战,我们在此通过[Mn-NTA](NTA = 次氮基三乙酸)前驱体纳米线的聚合诱导原位生长并随后进行热处理过程来合成MnO@碳(MnO@C)纳米线。研究了[Mn-NTA]前驱体纳米线的生长机制。前驱体纳米线的形态在很大程度上取决于MnCl2与NTA反应物的摩尔比。在摩尔比为2时,[Mn-NTA]纳米线的长度达到140多微米。此外,将合成的MnO@C纳米线与极低含量的还原氧化石墨烯(rGO)结合,制备了一种无需粘结剂的用于锂离子电池的自立式纸状MnO@C/rGO负极。MnO@C/rGO负极呈现出一种独特的结构,一维多孔MnO纳米线被导电碳框架分层包裹。结果,该自立式电极在100 mA g-1的电流密度下循环100次后实现了1368 mA h g-1的高容量,并具有出色的循环稳定性,即使在2000 mA g-1下循环1700次后仍具有689.9 mA h g-1的容量。