臺灣博碩士論文加值系統

本研究製備鋰離子混合式電容器之負極材料，以高能量行星式球磨機製備邊緣羧化石墨烯再以無電電鍍方式鍍上錫並發現電性較差、邊緣羧化石墨烯堆疊層數較多、邊緣氧化影響電性，使邊緣羧化石墨烯鍍氧化錫無法有效利用。因次另外球磨不同金屬硫化物的複合材料做為負極材料，並藉由金屬與鋰的合金反應以及硫的高電容量來做為球磨材料的選擇依據，球磨MoS2/graphite、Sn/MoS2/graphite、Sb2S3/graphite、MgS/graphite搭配1M LiPF6 in EC:DEC:DMC=1:1:1 (Vol%)有機電解液組成電化學儲能電池，並以恆電流充、放電測量分析負極材料之電化學性能，研究之初即考慮以低製備成本及簡易製備流程來達到競爭力。
本研究主要使用高效能行星式球磨機來製備負極材料，在球磨罐中放置乾冰使其昇華成二氧化碳來達到提供高壓二氧化碳的球磨環境，再與石墨球磨製備邊緣羧化石墨烯(ECG)，並以傅立葉轉換紅外光譜分析其碳氧的鍵結方式，以及使用拉曼分析其D band 與G band 比值來探討石墨化程度以及結構上破壞程度，用元素分析分析碳氧比以及使用EDS分析以無電電鍍還原錫(ECG/SnO2)的比例，再來與直接球磨MoS2/graphite、Sn/MoS2/graphite、Sb2S3/graphite、MgS/graphite 材料進行恆電流充、放電測量分析比較，可以發現ECG/SnO2在第二圈及第三圈放電電容量為190 mAhg-1和180 mAhg-1，MoS2/graphite在第二圈及第三圈放電電容量450 mAhg-1和400 mAhg-1，Sn/MoS2/graphite在第二圈及第三圈放電電容量560 mAhg-1和475mAhg-1，Sb2S3/graphite在第二圈及第三圈放電電容量 420 mAhg-1和240 mAhg-1而MgS/graphite在第二圈及第三圈放電電容量380 mAhg-1和300 mAhg-1。

We study the compositions of several negative electrodes for lithium hybrid capacitor and their capacities. The negative electrodes are loaded with oxide and chalcogenides mixed with graphite, which have undergone high-energy (satellite) ball milling. Selection of electrode active materials involves the cost consideration and their potentials in application right from the start. We have spent a significant amount of time preparing the edge carboxylated graphene (ECG) through ball milling, following by coating of tin metal with electroplating. Unfortunately, the product of ECG/SnO2 is less conductive and edge oxidation makes tin oxide fall off easily. Therefore, we switch to other compositions and search for conversion electrodes suitable for future research. The compositions being ball milled include MoS2/graphite, Sn/MoS2/graphite, Sb2S3/graphite, MgS/graphite. Their capacities are measured in the electrolyte of 1 M LiPF6 in EC:DEC:DMC=1:1:1 (vol%) electrolyte, using galvanostatic charge-discharge test.
Edge carboxylated graphene has been exfoliated through high energy ball milling in an environment filled with sublimed dry ice. Carbon dioxide is adsorbed on the edge of graphene such that the edge is carboxylated. The carbon-oxygen bonding is analyzed with Fourier transform infrared analysis. The graphene structure is studied with micro Raman. The carbon/oxygen ratio is measured using elemental analysis. The elemental ratio of ECG/SnO2 is measured with energy dispersive X-ray spectroscopy (EDS). The electrode capacity values are recorded as follows. The capacity of ECG/SnO2 is measured 190 mAhg-1 (2nd cycle) and 180 mAhg-1 (3rd cycle); that of MoS2/graphite is 450 (2nd cycle) and 400 mAhg-1 (3rd cycle); that of Sn/MoS2/graphite is 560 (2nd cycle) and 475 mAhg-1 (3rd cycle); that of Sb2S3/graphite is 420 (2nd cycle) and 240 mAhg-1 (3rd cycle); that of MgS/graphite is 380 (2nd cycle) and 300 mAhg-1 (3rd cycle).

 

We study the compositions of several negative electrodes for lithium hybrid capacitor and their capacities. The negative electrodes are loaded with oxide and chalcogenides mixed with graphite, which have undergone high-energy (satellite) ball milling. Selection of electrode active materials involves the cost consideration and their potentials in application right from the start. We have spent a significant amount of time preparing the edge carboxylated graphene (ECG) through ball milling, following by coating of tin metal with electroplating. Unfortunately, the product of ECG/SnO2 is less conductive and edge oxidation makes tin oxide fall off easily. Therefore, we switch to other compositions and search for conversion electrodes suitable for future research. The compositions being ball milled include MoS2/graphite, Sn/MoS2/graphite, Sb2S3/graphite, MgS/graphite. Their capacities are measured in the electrolyte of 1 M LiPF6 in EC:DEC:DMC=1:1:1 (vol%) electrolyte, using galvanostatic charge-discharge test.
Edge carboxylated graphene has been exfoliated through high energy ball milling in an environment filled with sublimed dry ice. Carbon dioxide is adsorbed on the edge of graphene such that the edge is carboxylated. The carbon-oxygen bonding is analyzed with Fourier transform infrared analysis. The graphene structure is studied with micro Raman. The carbon/oxygen ratio is measured using elemental analysis. The elemental ratio of ECG/SnO2 is measured with energy dispersive X-ray spectroscopy (EDS). The electrode capacity values are recorded as follows. The capacity of ECG/SnO2 is measured 190 mAhg-1 (2nd cycle) and 180 mAhg-1 (3rd cycle); that of MoS2/graphite is 450 (2nd cycle) and 400 mAhg-1 (3rd cycle); that of Sn/MoS2/graphite is 560 (2nd cycle) and 475 mAhg-1 (3rd cycle); that of Sb2S3/graphite is 420 (2nd cycle) and 240 mAhg-1 (3rd cycle); that of MgS/graphite is 380 (2nd cycle) and 300 mAhg-1 (3rd cycle).

 

摘要 I
目錄…………………………………………………………...III
圖目錄………………………………………………………...VI
表目錄………………………………………………………VIII
第一章 緒論 1
1.1 前言 1
1.2 研究動機 3
第二章 文獻回顧與理論基礎 4
2.1石墨電極材料 4
2.2 石墨烯製程方法 5
2.2.1機械剝離法 8
2.2.2 高效能機械球磨法 9
2.2.3溼式球磨法 10
2.2.4乾式球磨法 10
2.3 電容器 12
2.3.1 電化學電容器(Electrochemical capacitors, EC) 12
2.3.2 擬電容器 (Pseudocapacitor) 14
2.3.3 鋰離子混合式電容器 (Lithium-ion hybrid capacitors, LIHC)…………………………………………………………..16
2.3.4 鋰離子混合式電容器負極材料 16
2.3.5 鋰離子混合式電容器電解液 17

第三章 實驗方法與步驟 19
3.1 實驗藥品耗材與儀器設備 19
3.1.1 負極材料製備 19
3.1.2 電性量測 21
3.1.3 電化學測試儀器及設備 23
3.1.4 材料鑑定及分析之儀器 錯誤! 尚未定義書籤。
3.2 實驗流程 24
3.2.1 製備邊緣羧化石墨烯(ECG)實驗流程 24
3.2.2 ECG/SnO2合成流程 24
3.2.3 MoS2/graphite合成流程 25
3.2.4 Sn/MoS2/graphite合成流程 25
3.2.5 Sb2S3/graphite合成流程 26
3.2.6 MgS/graphite合成流程 26
3.2.7 電極製備流程 27
3.3 實驗步驟 27
3.3.1 製備邊緣羧化石墨烯(ECG)實驗步驟 27
3.3.2 ECG/SnO2合成步驟 28
3.3.3 MoS2/graphite合成步驟 29
3.3.4 Sn/MoS2/graphite合成步驟 299
3.3.5 Sb2S3/graphite合成步驟 30
3.3.6 MgS/graphite合成步驟 31
3.3.7 漿料製備步驟 32
3.3.8 電流收集器清洗及準備工作 32
3.4 電極材料鑑定與分析 33
3.4.1 場發射掃瞄式電子顯微鏡 33
3.4.2 拉曼光譜 33
3.4.3 X光繞射分析 34
3.4.4 傅立葉轉換紅外光譜分析(FTIR) 35
3.4.5 元素分析儀 36
3.4.6 恆電流充、放電量測 36
第四章 結果與討論 38
4.1 邊緣羧化石墨烯(Edge-Carboxylated Graphene)材料分析 38
4.1.1 傅立葉轉換紅外光譜(FTIR)分析 38
4.1.2 元素分析(Elemental Analysis) 40
4.1.3 RAMAN分析 41
4.1.4 XRD分析 44
4.2 SnO2/ECG材料分析 46
4.2.1 SnO2/ECG XRD分析 46
4.2.2 ECG/SnO2之形貌 48
4.2.3 ECG/SnO2 成分分析 49
4.2.4 SnO2/ECG單電極充、放電行為 50
4.3 材料MoS2/graphite和Sn/MoS2/graphite材料分析 54
4.3.1 MoS2/graphite恆電流充、放電分析 54
4.3.2 Sn/MoS2/graphite恆電流充、放電分析 56
4.4 材料Sb2S3/graphite材料分析 58
4.4.1 XRD 分析 58
4.4.2 恆電流充、放電分析 59
4.5 材料MgS/graphite材料分析 61
4.5.1XRD 分析………………………………………………..61
4.5.2 恆電流充、放電分析 62
4.5.3 循環伏安分析…………………………………………..64
第五章 結論 66

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