黑磷量子点的制备、稳定化及应用

P PREPARATION, STABILIZATION AND APPLICATION OFBLACK PHOSPHORUS QUANTUM DOTS

郭韩玉

11649149

硕士

材料工程

邓永红

2018-06-04

2018-06-23

哈尔滨工业大学

深圳

黑磷作为二维材料中的一员，由于其低维效应而引起广泛关注。与黑磷纳米片相比，黑磷量子点由于量子限域效应和边缘效应而表现出独特的电子和光学性质。黑磷量子点（BPQDs）具有增强的可饱和性吸收反应。但其在空气中极度不稳定，易与氧气（O2）和水（H2O）在光的催化下生成磷的氧化物，进而产生磷酸，从而影响黑磷量子点有效应用。本文通过电化学插层结合有机液相剥离法制备黑磷量子点，分散性好，尺寸均一，横向尺寸为 3.25 ±1.25 nm。在此基础上，通过静电纺丝技术制备 BPQDs /聚甲基丙烯酸甲酯（PMMA）复合纳米纤维薄膜，利用 PMMA 纳米纤维薄膜稳定 BPQDs。研究了 BPQDs/PMMA 复合纳米纤维薄膜作为锂离子电池负极材料的电化学性能，以 0.2 C 的倍率首圈放电比容量为 278 mAh g-1，循环 150 圈后，可获得 103 mAh g-1 的比容量。黑磷量子点可作为储锂的活性位点提供容量，虽然在充放电过程中由于黑磷量子点体积膨胀导致容量衰减，但稳定性远优于纯的黑磷或者 PMMA。BPQDs/PMMA 电极在 0.3 V 左右具有明显充放电平台，进一步证实黑磷量子点的存在。同时研究 了 BPQDs/PMMA 复合 纳米纤 维薄膜的 非线性 光 学性质 。BPQDs/PMMA 复合纳米纤维膜显示了从可见光（400 nm）到中红外光（至少1930 nm）的非线性光学响应。该结果表明 BPQDs/PMMA 复合纳米纤维膜可以改善黑磷在空气中易氧化的缺点，同时保持黑磷固有光学特性。以上结果表明，静电纺丝技术制备 BPQDs/PMMA 复合纳米纤维薄膜是有效的黑磷量子点稳定化策略，可为黑磷量子点在电化学和光学领域上的应用提供可行性。特别是将黑磷量子点应用在环境友好，可持续，高性能的能量获取、转换和存储系统中，包括太阳能电池，离子电池，超级电容器和燃料电池，可 以解决非可再生能源的急速消耗、日益严峻的环境污染等问题。

As a member of two-dimensional materials, black phosphorus has attracted wide attention due to its low dimensional effect. Compared with black phosphorus nanosheets, black phosphorus quantum dots exhibit unique electronic and optical properties due to quantum confinement and edge effects. Black phosphorus quantum dots (BPQDs) have enhanced saturable absorption reactions. However, it is extremely unstable in the air, and it is easy to generate oxides of phosphorus under the catalysis of oxygen (O2) and water (H2O), thereby generating phosphoric acid and affecting the effective application of the properties of the black phosphorus quantum dots. In this paper, black phosphorus quantum dots were prepared by electrochemical intercalation combined with organic liquid stripping method. The dispersion was good, the size was uniform, and the transverse dimension was 3.25 ±1.25 nm. On this basis, BPQDs/PMMA composite nanofiber membranes were prepared by electrospinning, and PMMA nanofiber membranes were used to stabilize the black phosphorus quantum dots (BPQDs). The electrochemical performance of BPQDs/PMMA composite nanofiber membranes as anode materials for lithium-ion batteries was studied. The specific capacity of the first cycle discharge at 0.2 C was 278 mAh g-1. After 150 cycles, 103 mAh g-1 was obtained. The black phosphorus quantum dots can provide capacity as active sites for lithium storage. Although the capacity of the black phosphorus quantum dots expands during charge and discharge, the stability is much better than pure black phosphorus or PMMA. The BPQDs/PMMA electrode had a significant charge and discharge plateau around 0.3 V, further confirming the existence of black phosphorus quantum dots. At the same time, the nonlinear optical properties of BPQDs/PMMA composite nanofiber films were studied. The BPQDs/PMMA composite nanofiber membranes exhibit a nonlinear optical response from visible light (400 nm) to mid-infrared light (at least 1930 nm). These results indicate that BPQDs/PMMA composite nanofiber membranes can improve the disadvantages of black phosphorus in air oxidation, while maintaining the inherent optical and electrochemical properties of black phosphorus. The results show that the preparation of BPQDs/PMMA composite nanofiber membrane by electrospinning technology is an effective strategy for the stabilization of black phosphorus quantum dots, which can provide feasibility for the application of black phosphorus quantum dots in the fields of electrochemistry and optics. In particular, the black phosphorus quantum dots is used in storage systems which are environmental friendly, sustainable, and high-performance energy acquisition, conversion, including solar cells, ion batteries, super capacitors, and fuel cells. Itcan solve the problems of rapid consumption of non-renewable energy and increasingly severe environmental pollution.

黑磷量子点 静电纺丝 聚甲基丙烯酸甲酯 锂离子电池 光学应用

black phosphorus quantum dots electrospinning poly(methyl methacrylate) lithium ion battery optical applications

中文

联合培养

南方科技大学

郭韩玉. 黑磷量子点的制备、稳定化及应用[D]. 深圳. 哈尔滨工业大学,2018.