電容去離子(Capacitive Deionization, CDI)技術為一種低能耗、低成本及對環境無二次污染的離子分離技術。農漁業廢棄物轉化為生物質衍生活性碳的研究及應用具有發展前景，為探討動物基與植物基的材料於製成生物質衍生活性碳之差異性，本研究使用虱目魚鱗或稻殼作為材料，虱目魚鱗以700°C、800°C、900°C 三種活化溫度製備生質活性碳，稻殼則以800°C與1:1、1:2的活化劑(NaOH)比例製備生質活性碳，比較各生質活性碳之物理結構和電化學特性上的差異，並運用於電容去離子(CDI)系統中，並與市售活性碳比較對離子去除效能的表現。
    魚鱗活性碳(FSAC)的比表面積與孔體積會隨著活化溫度上升而增加，稻殼活性碳(RHAC)則隨著活化劑比例的提高而增加，FSAC900與RHAC800 1:2的比表面積可達1945.79 m2/g與933.44 m2/g，孔體積可達1.68 cm3/g與0.65 cm3/g。以CV與EIS分析材料的電化學特性，發現FSAC900與RHAC800 1:2在掃描速率為1 mV/s 時，表現出73.75 F/g與66.25 F/g的高比電容值，電荷轉移電阻分別為1.37 Ω與3.55 Ω，擴散電阻則為7.25×10-6 Ω與2.25 Ω。
    將FSAC、RHAC與市售活性碳應用於CDI系統中，發現兩種生質活性碳對於Na+的吸附能力皆優於Cl-，且FSAC與RHAC對Na+的平均電吸附量皆高於GAC；但在Cl-的吸附能力上，FSAC與RHAC的平均電吸附量皆略低於GAC。本研究顯示生物質衍生活性碳應用於CDI系統之發展潛力。

Capacitive Deionization (CDI) technology, as a novel ion separation method, is characterized by low energy consumption, low cost, and no secondary environmental pollution. Researches and applications of converting agricultural and fishery wastes into biomass-derived activated carbons have shown promising prospects. To explore the differences between animal-based and plant-based materials in synthesizing biomass-derived activated carbons, this study employed milkfish scales and rice husks as raw materials. The milkfish scales were processed with activation temperatures of 700°C, 800°C, or 900°C, while the rice husks were activated at 800°C with two ratios of activation agents (NaOH). This study compared the physical structures and electrochemical properties of the synthesized biomass-derived activated carbons with commercial activated carbon and applied them in the CDI system to compare the ion removal efficiency.
    The specific surface area and pore volume of fish scale activated carbon (FSAC) increase with higher activation temperatures, while those of rice husk activated carbon (RHAC) increase with higher ratios of activation agents. The specific surface areas of FSAC900 and RHAC800 1:2 can reach 1945.79 m²/g and 933.44 m²/g, respectively, with pore volumes of 1.68 cm³/g and 0.65 cm³/g. Electrochemical properties of FSAC and RHAC were analyzed using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). FSAC900 and RHAC800 1:2 exhibited high specific capacitance values of 73.75 F/g and 66.25 F/g at 1 mV/s, respectively. Their charge transfer resistances were 1.37 Ω and 3.55 Ω, and their diffusion resistances were 7.25×10⁻⁶ Ω and 2.25 Ω, respectively.
When applying FSAC, RHAC, or commercial activated carbon in the CDI system, it was found that both types of biomass-derived activated carbons exhibited better electrosorption capacity for Na+ than that for Cl-. FSAC and RHAC produced at different activation temperatures or with different ratios of activation agents showed a higher average electrosorption capacity for Na+ compared to GAC. However, for Cl- electrosorption, the average electrosorption capacity of both FSAC and RHAC was slightly lower than that of GAC. This study demonstrated the biomass-derived activated carbons applied in CDI system has great development potential.

目錄
中文摘要	i
英文摘要	ii
目錄	iv
List of Figure	vii
List of Table	xi
第一章	緒論	1
1.1	研究緣起	1
1.2	研究目的	2
第二章	文獻回顧	3
2.1	海水淡化技術	3
2.1.1	薄膜法	4
2.1.2	蒸餾法	8
2.1.3 電容去離子技術(Capacitive Deionization, CDI)	11
2.2	電容去離子技術	12
2.2.1	電容去離子技術原理	12
2.2.2	電雙層電容	14
2.2.3	電極材料之選擇	16
2.3	活性碳	18
2.3.1	生物質衍生活性碳	19
2.3.2	魚鱗衍生活性碳	20
2.3.3	稻殼衍生活性碳	21
第三章	研究方法及材料	22
3.1	實驗架構	22
3.2	實驗藥品與設備	24
3.2.1	實驗藥品	24
3.2.2	實驗設備	25
3.3	電極材料製備	26
3.3.1	魚鱗活性碳(Fish Scale Activated Carbons, FSAC)	26
3.3.2	稻殼活性碳(Rice Husk Activated Carbons, RHAC)	26
3.4	電極製備	27
3.4.1	循環伏安法電極製備	27
3.4.2	CDI電極製備	27
3.5	實驗分析方法	28
3.5.1	X射線繞射分析(X-ray Diffraction, XRD)	28
3.5.2	熱重分析(Thermogravimetric analysis, TGA)	28
3.5.3    比表面積與孔徑分析(Surface Area and Pore size distribution Analyzer) 	29
3.5.4	掃描式電子顯微鏡分析(Scanning Electron Microscope, SEM)	29
3.5.5    表面官能基分析(Fourier-transform infrared spectroscopy, FTIR) 	29
3.5.6	接觸角分析(Contact Angle, CA)	30
3.5.7	循環伏安法分析(Cyclic Voltammetry, CV)	30
3.5.8    電化學阻抗分析 (Electrochemical impedance spectroscopy, EIS)	31
3.6.1	電容去離子實驗(Capacitive Deionization Experiment, CDI)	32
3.6.2	感應耦合電漿光譜儀(Inductively coupled plasma atomic emission spectroscopy, ICP-OES)	33
3.6.3	離子層析儀(Ion chromatograph, IC)	34
第四章	結果與討論	36
4.1	魚鱗活性碳(Fish Scale Activated Carbon, FSAC)	36
4.1.1	虱目魚魚鱗熱重分析	36
4.1.2	魚鱗活性碳表面特性分析	38
4.1.3	魚鱗活性碳電化學特性分析	50
4.1.4	魚鱗活性碳應用於電容去離子技術	56
4.2	稻殼活性碳(Rice Husk Activated Carbon, RHAC)	66
4.2.1	稻殼熱重分析	66
4.2.2	稻殼活性碳表面特性分析	68
4.2.3	稻殼活性碳電化學特性分析	80
4.2.4	稻殼活性碳應用於電容去離子技術	86
4.3	虱目魚鱗與稻殼生質活性碳比較	94
4.3.1	物理結構特性	94
4.3.2	電化學特性分析	97
4.3.3	電容去離子系統	100
第五章	結論與建議	104
Reference	106
 
List of Figure
Figure 2.1.1.1 Diagram of reverse osmosis (RO) principle (Miller, 2003).	5
Figure 2.1.1.2 Schematic diagram of electrodialysis (ED) desalination process (Miller, 2003).	6
	7
Figure 2.1.1.3 Schematic diagram of forward osmosis (FO) process	7
(Islam et al., 2018).	7
Figure 2.1.2.1 Schematic diagram of multi-effect distillation (MED) process	9
(Curto et al., 2021).	9
Figure 2.1.2.2 Schematic diagram of multi-stage flash (MSF) process	10
(Curto et al., 2021).	10
Figure 2.2.1.1 Schematic diagram of the electrosorption/desorption process in CDI (Sayed et al., 2023).	13
Figure 2.2.2.1 Schematic of the Electric Double Layer (EDL) (Kopeliovich, 2023).	15
Figure 2.2.3.1 (a) Pore nomenclature according to IUPAC, (b) nomenclature in porous media transport theory (Porada et al., 2013).	17
Figure 3.1.1 Schematic research structure for FSAC or RHAC applied in CDI system.	23
Figure 3.6.1.1 Schematic diagram of CDI system.	35
Figure 4.1.1.1 Thermogravimetric analysis (TGA) of fish scale powder.	37
Figure 4.1.2.1 XRD patterns of original fish scale and fish scale activated carbons.	40
Figure 4.1.2.2 SEM images of the original fish scale powder (a) x 1 K X, (b) blocky structure x 3 K X, (c) strip structure x 4 K X, (d) fold structure x 10 K X.	41
Figure 4.1.2.3 SEM images of the FSACs. (a) FSAC900 x 5 K X, (b) FSAC800 x 5 K X, (c) FSAC700 x 5 K X, (d) FSAC900 x 30 K X, (e) FSAC800 x 30 K X, (f) FSAC700 x 30 K X.	42
Figure 4.1.2.4 Nitrogen adsorption (●) - desorption (▲) isotherms of the fish scale activated carbons and GAC (a) FSAC900, (b) FSAC800, (c) FSAC700, and (d) GAC.	43
Figure 4.1.2.5 Pore size distribution of the fish scale activated carbons and GAC (a) FSAC900, (b) FSAC800, (c) FSAC700, and (d) GAC.	44
Figure 4.1.2.6 FT-IR spectra of (a) FSP, (b) FSAC900, (c) FSAC800 and (d) FSAC700.	47
Figure 4.1.2.7 The comparison of FT-IR spectra of FSAC900, FSAC800, FSAC700, and FSP.	48
Figure 4.1.2.8 Contact angles of FSAC electrode (a) FSAC900, (b) FSAC800, and (c) FSAC700.	49
Figure 4.1.3.1 Cyclic voltammograms of (a) FSAC900, (b) FSAC800, (c) FSAC700, and (d) GAC in 1 M NaCl with various scan rates.	52
Figure 4.1.3.2 Specific capacitance (F/g) of the FSAC900, FSAC800, FSAC700, and GAC electrode in 1 M NaCl at different scan rates.	53
Figure 4.1.3.3 The electrochemical impedance spectra (EIS) measured at frequency range of 0.1 Hz to 105 Hz of the (a) FSAC900, (b) FSAC800, (c) FSAC700 electrode in 1 M NaCl with curve fitting.	54
Figure 4.1.3.4 The electrochemical impedance spectra (EIS) measured at frequency range of 0.1 Hz to 105 Hz of the FSAC900, FSAC800, FSAC700 and GAC electrode in 1 M NaCl.	55
Figure 4.1.4.1 Electrosorption/desorption limits test of sodium ions in FSAC800 with 200 mg/L sodium chloride.	59
Figure 4.1.4.2 Electrosorption/desorption limits test of chloride ions in FSAC800 with 200 mg/L sodium chloride.	59
Figure 4.1.4.3 Changes of conductivity during electrosorption/desorption processes with FSAC900, FSAC800, FSAC700 electrodes applied in CDI system.	60
Figure 4.1.4.4 Changes of sodium concentration during electrosorption/desorption processes with FSAC900, FSAC800, FSAC700 applied in CDI system.	61
Figure 4.1.4.5 Changes of chloride concentration during electrosorption/desorption process with FSAC900, FSAC800, FSAC700 applied in CDI system.	61
Figure 4.1.4.6 Electrosorption capacity of sodium with FSAC900, FSAC800, FSAC700, and GAC in four cycles of CDI system.	64
Figure 4.1.4.7 Electrosorption capacity of chloride with FSAC900, FSAC800, FSAC700, and GAC in four cycles of CDI system.	64
Figure 4.2.1.1 Thermogravimetric analysis (TGA) of rice husk powder.	67
Figure 4.2.2.1 XRD patterns of original rice husk and rice husk activated carbons.	70
Figure 4.2.2.2 SEM images of the original rice husk powder. (a) x 500 X, (b) flaky structure x 1 K X, (c) strip structure x 5 K X, (d) planar structure x 5 K X.	71
Figure 4.2.2.3 SEM images of the RHACs. (a) RHAC800 1:2 x 5 K X, (b) RHAC800 1:1 x 5 K X, (c) RHAC800 1:2 x 30 K X, (d) RHAC800 1:1 x 30 K X.	72
Figure 4.2.2.4 Nitrogen adsorption (●) - desorption (▲) isotherms of the rice husk activated carbons and GAC (a) RHAC800 1:2, (b) RHAC800 1:1, and (c) GAC.	73
Figure 4.2.2.5 Pore size distribution of the rice husk activated carbons and GAC (a) RHAC800 1:1, (b) RHAC800 1:2, and (c) GAC.	74
Figure 4.2.2.6 FT-IR spectra of (a) RHP, (b) RHAC800 1:2, and, (c) RHAC800 1:1.	77
Figure 4.2.2.7 The comparison of FT-IR spectra of RHAC800 1:2, RHAC800 1:2, and RHP.	78
Figure 4.2.2.8 Contact angles of RHAC electrode (a) RHAC800 1:2, (b) RHAC800 1:1.	79
Figure 4.2.3.1 Cyclic voltammograms of (a) RHAC800 1:2, (b) RHAC800 1:1, and (c) GAC in 1 M NaCl with various scan rates.	82
Figure 4.2.3.2 Specific capacitance (F/g) of the RHAC800 1:2, RHAC800 1:2, and GAC electrode in 1 M NaCl at different scan rates.	83
Figure 4.2.3.3 The electrochemical impedance spectra (EIS) measured at frequency range of 0.1 Hz to 105 Hz of the (a) RHAC800 1:2, (b) RHAC800 1:1 electrode in 1 M NaCl with curve fitting.	84
Figure 4.2.3.4 The electrochemical impedance spectra (EIS) measured at frequency range of 0.1 Hz to 105 Hz of the RHAC800 1:2, RHAC800 1:1, and GAC electrode in 1 M NaCl.	85
Figure 4.2.4.1 Electrosorption/desorption limits test of RHAC800 1:1 with 200 mg/L sodium chloride.	88
Figure 4.2.4.2 Changes of conductivity during electrosorption/desorption processes with RHAC800 1:1, RHAC800 1:2 electrodes applied in CDI system.	88
Figure 4.2.4.3 Sodium concentration changes during electrosorption/desorption process with RHAC800 1:1, RHAC800 1:2 electrodes applied in CDI system.	89
Figure 4.2.4.4 Chloride concentration changes during electrosorption/desorption process with RHAC800 1:1, RHAC800 1:2 electrodes applied in CDI system.	89
Figure 4.2.4.5 Electrosorption capacity of sodium with RHAC800 1:2, RHAC800 1:1, and GAC in four cycles of CDI system.	93
Figure 4.2.4.6 Electrosorption capacity of chloride with RHAC800 1:2, RHAC800 1:1, and GAC in four cycles of CDI system.	93
Figure 4.3.2.1 Cyclic voltammograms of FSAC900 and RHAC800 1:2 in 1 M NaCl at 1 mV/s scan rate.	98
Figure 4.3.2.2 The electrochemical impedance spectra (EIS) measured at frequency range of 0.1 Hz to 105 Hz of the FSAC900 and RHAC800 1:2 electrode in 1 M NaCl.	99
Figure 4.3.3.1 Sodium concentration changes during electrosorption/desorption process with FSAC900 and RHAC800 1:2 electrodes applied in CDI systems.	101
Figure 4.3.3.2 Chloride concentration changes during electrosorption/desorption process with FSAC900 and RHAC800 1:2 electrodes applied in CDI systems.	101
Figure 4.3.3.3 Electrosorption capacity of sodium during four cycles of CDI process with FSAC900 and RHAC800 1:2 electrodes.	103
Figure 4.3.3.4 Electrosorption capacity of chloride during four cycles of CDI process with FSAC900 and RHAC800 1:2 electrodes.	103
 
List of Table
Table 3.2.1.1 Manufactures and purity of experimental chemical.	24
Table 3.2.2.1 Manufactures and models of experimental equipment.	25
Table 4.1.2.1 Porosity characteristics of the FSACs and GAC.	45
Table 4.1.2.2 FTIR functional groups of FSACs and fish scale powder.	48
Table 4.1.3.1 Specific capacitance (F/g) of FSACs and GAC electrode in 1 M NaCl at different scan rates.	53
Table 4.1.3.2 Impedance analyses of FSAC 900, FSAC800, FSAC700, and GAC in 1
M NaCl based on equivalent circuit model.	55
Table 4.1.4.1 The removal efficiency (%) and electrosorption capacity of sodium with FSAC900, FSAC800, FSAC700, and GAC applied in CDI system with 200 mg/L NaCl.	62
Table 4.1.4.2 The removal efficiency (%) and electrosorption capacity of chloride with FSAC900, FSAC800, FSAC700, and GAC applied in CDI system with 200 mg/L NaCl.	63
Table 4.1.4.3 The calculated theoretical conductivity contributions of sodium, chloride and total carbon during electrosorption/desorption with FSAC900.	65
Table 4.2.2.1 Porosity characteristics of the RHACs and GAC.	75
Table 4.2.2.2 FTIR functional groups of RHACs and rice husk powder.	78
Table 4.2.3.1 Specific capacitance (F/g) of RHACs and GAC electrode in 1 M NaCl at different scan rates.	83
Table 4.2.3.2 Impedance analyses of RHAC800 1:2, RHAC800 1:1, and GAC in 1	85
M NaCl based on equivalent circuit model.	85
Table 4.2.4.1 The removal efficiency (%) and electrosorption capacity of sodium chloride with RHAC800 1:1, RHAC800 1:2, and GAC applied in CDI system with 200 mg/L NaCl.	90
Table 4.2.4.2 The removal efficiency (%) and electrosorption capacity of sodium with RHAC800 1:1, RHAC800 1:2, and GAC applied in CDI system with 200 mg/L NaCl.	91
Table 4.2.4.3 The removal efficiency (%) and electrosorption capacity of chloride with RHAC800 1:1, RHAC800 1:2, and GAC applied in CDI system with 200 mg/L NaCl.	92
Table 4.3.1.1 Porosity characteristics of various biomass-derived activated carbons.	96
Table 4.3.1.2 The yield of FSACs and RHACs.	96
Table 4.3.2.1 Specific capacitance (F/g) of FSAC900 and RHAC800 1:2 electrode in 1 M NaCl with various scan rates.	98
Table 4.3.2.2 Impedance analyses of FSAC900 and RHAC800 1:2 in 1 M NaCl based on equivalent circuit model.	99
Table 4.3.2.3 Porosity characteristics of FSAC900 and RHAC800 1:2.	99
Table 4.3.3.1 The removal efficiency (%) and electrosorption capacity of sodium with
FSAC900 and RHAC800 1:2 applied in CDI system with 200 mg/L NaCl.	102
Table 4.3.3.2 The removal efficiency (%) and electrosorption capacity of chloride with FSAC900 and RHAC800 1:2 applied in CDI system with 200 mg/L NaCl.	102

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