中文摘要

本研究最主要的目的，為開發低成本之LiFePO4/C複合陰極材料的製程。於本研究中已成功的利用溶膠-凝膠法，在短時間及低耗能下，合成出LiFePO4/C複合陰極材料，其中溶膠-凝膠法所使用的檸檬酸，在本製程中同時扮演螯合劑及複合材料中碳的來源，結果顯示，這些檸檬酸所產生的碳，不但可以增加複合材料的導電度，同時也可以抑制LiFePO4晶粒的成長，並成功合成出奈米尺度純相的LiFePO4。不同熱裂解-煆燒溫度下(450~950oC)，所得之LiFePO4晶粒大小約在20~30nm之間。所得LiFePO4/C複合陰極材料之導電性隨著熱裂解-煆燒溫度之增加而提昇，但當煆燒溫度上升到950oC時，其導電性則會些微的下降，這是因為複合材料的碳含量及其石墨化程度之綜合影響。煆燒溫度在850oC時，所合成出來的LiFePO4/C複合陰極材料，具有最佳之電化學特性及導電度(10-3 S/cm-1)，且由結果發現，LiFePO4的循環特性與充放電速率程序有關，其中以經過低充放電速率活化過之LiFePO4材料，具有較佳的循環特性。

為了更進一步降低製程的成本，我們將溶膠-凝膠法中所使用的鐵鹽換成較低成本的鐵粉，同時利用X光吸收光譜的技術，對不同條件所得前驅物及其相對條件所得複合材料的局部結構與的氧化狀態進行分析，以深入探討其形成之機制。結果發現當R值(檸檬酸莫爾數與金屬離子總莫爾數之比值)為1及0.75時，鐵粉主要會氧化成二價的鐵離子，而當R值下降至0.5時，鐵粉則氧化成三價的鐵離子，雖然這些鐵離子，在熱裂解-煆燒過程中均會還原成二價的鐵離子，但是R值為1及0.75的前驅物，所熱裂解-煆燒成的LiFePO4，具有較佳的晶體有序結構，而R值為0.5的前驅物，所熱裂解-煆燒而成的LiFePO4之結晶結構有序化程度則較差。針對晶體繞射圖譜，以Riteveld法進行分析時，發現以R值為0.5的前驅物，熱裂解-煆燒所得的LiFePO4晶體之陽離子混合情形較嚴重，其與吸收光譜所得結果相吻合。另外，本研究中亦提出前驅物與合成的LiFePO4粉末的結構示意圖。

由上述之結果得知，鐵粉會氧化成二價鐵離子，依R值之大小，會有不同程度之二價鐵離子和溶氧繼續反應成三價的鐵離子，降低合成材料之有序化程度，影響其電化學性能。為了能夠提升LiFePO4的充放電性能，本研究針對不同R值合成的LiFePO4/C複合材料的電化學特性及材料特性進行探討。在R值為1、0.75與0.5所合成的LiFePO4的碳含量為10%、8%及5%，而在熱裂解-煆燒過程中所生成的碳，可以均勻地分布在LiFePO4的結構中與晶粒之間，雖然將R值提升至1時，所合成的LiFePO4/C複合陰極材料的導電度會有所提升，但是太多的碳，也同時阻礙了鋰離子的擴散路徑。而當R值下降至0.5時，由於含碳量的下降，而導致複合陰極材料的導電度下降，而當R值為0.75時，所合成的複合材料之含碳量最適當，且LiFePO4晶體具有較佳之有序化，在室溫及1/40C的充放電速率時，具有最高的放電電容量(153 mAh/g)。顯示，LiFePO4晶體之有序化程度與存在LiFePO4的結構與晶粒之間的含碳量及其型態對電化學特性影響，值得進一步深入了解與探討。

Abstract

The main objective of this work is to develop a low cost process for the synthesis of LiFePO4/carbon composite cathode materials. The LiFePO4/carbon composite cathode materials were successfully synthesized by a developed sol–gel process. The citric acid in the developed sol–gel process plays the role not only as a complexing agent but also as a carbon source, which improves the conductivity of the composites and hinders the growth of LiFePO4 particles. The nano-sized LiFePO4 particles without the impurity phase were successfully synthesized. The grain size of LiFePO4 particles in the range of 20~30 nm is obtained at calcined temperatures from 450 to 850 oC. Increasing the calcination temperature leads to a decrease in the carbon content but an increase in the conductivity of the composites in the range of 400–850 oC. However, the conductivity slightly decreases if the calcination temperature further increases to 950 oC. The LiFePO4/carbon composite synthesized at 850 oC shows the highest conductivity (10-3 S cm-1), the highest specific capacity, and the best rate capability among the synthesized materials. It is worthy to note that the cell performance of the LiFePO4 depends on the electrochemical cycling procedure employed.

To further reduce the cost of raw materials, iron salts were replaced by iron powders in the sol-gel process. The local structure and oxidation state of the precursors and the LiFePO4/C composite powders were investigated by X-ray absorption spectroscopy (XAS) to provide a deep insight into their formation mechanism. It was found that the oxidation states of iron in the precursors for R = 1 and 0.75 consist mainly of Fe(II) and traces of Fe(III). However, the oxidation state of iron in the precursor for R = 0.5 comprises mainly of Fe(III). The oxidation state of iron in all pyrolysis-sintered powders is Fe(II). The structure of the precursors and the sintered powders for R = 1 and 0.75 is more ordering than that for R = 0.5. It is consistent with the observation of the cation mixing from the Riteveld analysis of the XRD patterns. It is one of reason responsible for the better electrochemical performance of the LiFePO4/C composite material prepared at higher R. The structural scheme of the precursors and the sintered powders are proposed in this work.

The iron powders were oxidized to Fe2+ ions which may be complexed with citric acid or be further oxidized to Fe3+ ions by the dissolved oxygen. The effect of the molar ratio of citric acid to total metal ions (R) on the structural and electrochemically properties of the synthesized compounds was studied. It is necessary to achieve an optimal amount of carbon for the synthesis of LiFePO4/C composite materials with good rate capability. The carbon contents for the samples synthesized at the molar ratio of citric acid to total metal ions of 1, 0.75 and 0.5 are 10, 8, and 5 wt%, respectively. The in situ formation of the carbon can uniformly distributed between LiFePO4 inter/intra particle. Increasing the carbon content (R=1) leads to increase the electronic conductivity but impede the Li+ ion diffusion path of the composite materials. However, decreasing the carbon content (R= 0.5) leads to decrease the electronic conductivity of the composite materials. The carbon content and distribution between LiFePO4 inter/intra particle must be given careful attention. The molar ratio of citric acid to total metal ions “R” should not be too high or too low. Samples with R (0.75) exhibited the highest initial capacity, about 153 mAh/g when cycled at 1/40 C rate at room temperature.

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