Saji Viswanathan S, Song Hyun-Kon
J Nanosci Nanotechnol. 2015 Jan;15(1):734-41. doi: 10.1166/jnn.2015.9173.
Electrode materials having nanometer scale dimensions are expected to have property enhancements due to enhanced surface area and mass/charge transport kinetics. This is particularly relevant to intrinsically low electronically conductive materials such as lithium iron phosphate (LiFePO4), which is of recent research interest as a high performance intercalation electrode material for Li-ion batteries. Many of the reported works on LiFePO4 synthesis are unattractive either due to the high cost of raw materials or due to the complex synthesis technique. In this direction, synthesis of LiFePO4 directly from inexpensive FePO4 shows promise.The present study reports LiFePO4 nanostructures prepared from iron (III) phosphate (FePO4 x 2H2O) by precipitation-hydrothermal method. The sintered powder was characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), Inductive coupled plasma-optical emission spectroscopy (ICP-OES), and Electron microscopy (SEM and TEM). Two synthesis methods, viz. bulk synthesis and anodized aluminum oxide (AAO) template-assisted synthesis are reported. By bulk synthesis, micro-sized particles having peculiar surface nanostructuring were formed at precipitation pH of 6.0 to 7.5 whereas typical nanosized LiFePO4 resulted at pH ≥ 8.0. An in-situ precipitation strategy inside the pores of AAO utilizing the spin coating was utilized for the AAO-template-assisted synthesis. The template with pores filled with the precipitate was subsequently subjected to hydrothermal process and high temperature sintering to fabricate compact rod-like structures.
由于表面积增加以及质量/电荷传输动力学增强,预计具有纳米尺度尺寸的电极材料会有性能提升。这对于本质上电子导电性低的材料(如磷酸铁锂(LiFePO₄))尤为重要,磷酸铁锂作为锂离子电池的高性能插层电极材料,是近期的研究热点。许多已报道的磷酸铁锂合成方法,要么因原材料成本高,要么因合成技术复杂,而缺乏吸引力。在这个方向上,直接由廉价的磷酸铁合成磷酸铁锂显示出了前景。本研究报道了通过沉淀 - 水热法由磷酸铁(III)(FePO₄·2H₂O)制备的磷酸铁锂纳米结构。对烧结粉末进行了X射线衍射(XRD)、X射线光电子能谱(XPS)、电感耦合等离子体发射光谱(ICP - OES)以及电子显微镜(SEM和TEM)表征。报道了两种合成方法,即本体合成和阳极氧化铝(AAO)模板辅助合成。通过本体合成,在沉淀pH值为6.0至7.5时形成了具有特殊表面纳米结构的微米级颗粒,而在pH≥8.0时得到了典型的纳米级磷酸铁锂。利用旋涂在AAO孔内进行原位沉淀策略用于AAO模板辅助合成。随后对填充有沉淀物的孔的模板进行水热过程和高温烧结,以制备致密的棒状结构。