近年來普魯士藍材料被發現不但具有鋰電池方面的應用潛力，在另一種更為新穎的鈉電池方面亦然，因而成為研究焦點，原因在於該材料提供足夠大的晶格空隙，使得鋰離子得以進行嵌入遷出，而原子半徑更大的鈉離子亦可。本論文中的實驗樣品為Na-Fe-Fe普魯士藍，主要分成兩大部分。 第一部分為基本物理特性探討，利用X光繞射，發現合成時添加檸檬酸鈉能製造出monoclinic結構的普魯士藍，有別於以往的Cubic結構。透過紫外-可見光吸收光譜，發現monoclinic結構在680 nm具有些微的吸收峰位移，反映出其顏色與cubic結構不同。XPS分析顯示monoclinic結構的自旋態可能為Fe(II)HS，而cubic結構則是Fe(II)LS。拉曼光譜分析指出monoclinic結構具有異構物型態，即Fe(II)LS-CN-Fe(III)與Fe(II)HS-NC-Fe(III)兩者可能同時共存。交流磁化率與磁滯實驗顯示無論monoclinic或cubic結構皆為鐵磁性，意味著結構上的變異不至於改變其磁性。 第二部分為電測試，將Na-Fe-Fe樣品製成電池陰極極片後，搭配鋰金屬作為陽極，封裝成CR2032電池進行充放電分析。NF1電池首次充放電容量皆為60 mAh/g，經200次循環測試後皆衰減為43 mAh/g。NF2電池與NF1電池比較後發現特性相反，首次充放電容分別為6 mAh/g與2 mAh/g，但隨著循環次數增加而增加，到了第200次電容量皆上升為34 mAh/g。NF3電池首次充放電容量僅12 mAh/g，經200次循環後，發現損失情形不明顯。 ;Prussian Blue (PB) attracts many attentions recently for it’s application potential not only in the field of Lithium battery but also in Sodium battery, a novel one compared to the former, because it offers large enough voids at the center portion of the lattice to accommodate Lithium or Sodium ions. In this thesis, the Na-Fe-Fe PB has been studied and divided into two parts. The first part is the determination of physical property. A monoclinic phase of Na-Fe-Fe, differ from the traditional cubic one, was formed by introducing Sodium Citrate in fabrication process and confirmed by XRD. In UV-VIS experiment, the absorbance maxima of cubic and monoclinic phases are 680 and 670 nm respectively, which indicates the color difference of these two. The spin state of Fe(II) for monoclinic phase may be Fe(II)HS according to XPS measurement while in cubic phase it is Fe(II)LS. The isomer structure in monoclinic one was revealed form micro-Raman experiment. The possible picture for this may refers to the co-existent of Fe(II)LS-CN-Fe(III) and Fe(II)HS-NC-Fe(III) unit. From AC susceptibility, the magnetic respond was observed to be suppressed by applied field for all sample showing that there’s a fluctuation in every sample. The difference of structure phase won’t affect the magnetic nature was determined from M-H curve. The second part is battery testing. All Na-Fe-Fe sample was introduced as cathode and Lithium as anode in CR2032 battery. The capacity of NF1 battery in first cycle of charge and discharge were 60 mAh/g and decreased to 43 mAh/g after 200 cycles. The capacity of NF2 battery in first cycle were 6 mAh/g and 2 mAh/g. After 200 cycles, however, both increased to 34 mAh/g showing opposite properties to NF1. The capacity of NF3 battery in the first cycle were only 12 mAh/g but no significant change after 200 cycles.
