http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/29 Sat, 04 Apr 2026 07:39:43 GMT 2026-04-04T07:39:43Z http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/71091 標題: 黏著劑與碳包覆對鋰離子電池回收矽負極循環表現影響之研究; Binder and Carbon Coating Effects on Cycling Performances of Recycled-Silicon Negative Electrode for Lithium Ion Batteries 作者: Wei-Yan Chen; 陳維彥 摘要: 本研究是以太陽光電產業的切削矽泥與造紙產業之副產物作為鋰離子電池的負極材料。由於鋰嵌入矽的模式為合金化，雖然其單位質量之電容量相當優越，然而卻使材料產生劇烈的體積變化並帶來不利於電極循環的負面影響，像是矽粒子粉化、失去電性接觸、生成的固態電解質介面(Solid electrolyte interface, SEI)膜容易破裂。為了抑制上述的缺點，本研究將透過兩種方法進行矽電極的改善： (1) 使用不同種類的黏著劑與矽粒子及石墨導電劑結合，試圖尋找具有較佳黏附效果並能有效發揮活性材料電容量之黏著劑； (2) 結合矽粒子與碳前驅物(木質纖維素、木質素)製備碳矽複材，在矽粒子表面披覆碳層提升其導電性並有助於生成穩定的SEI膜進而提升循環表現。 在黏著劑方面，主要採用聚丙烯酸(PAA)、海藻酸鈉(Alg)等做為基底，並與丁苯橡膠(SBR)結合，實驗結果以PAA作為黏著劑之矽電極表現最佳，首圈嵌入與嵌出電容量分別為2738.8、2287.8 mAh/g Si+KS-6，庫倫效率為0.835，首圈的不可逆電容量僅有451 mAh/g Si+KS-6。本研究除了找出表現最優異的黏著劑外，亦透過自定義的黏著強度試驗(peel test)、電化學阻抗頻譜(EIS)探尋各黏著劑組合的矽電極電容量衰退原因。另外透過調整矽電極中矽與KS-6的比例，找出較能有效發揮矽電容量的比例，實驗結果顯示矽、KS-6、PAA混合比例為3:6:1時具有較佳的循環表現，其51圈的平均嵌出電容量為1025.9 mAh/g Si+KS-6，電容量保留率達70.0 %，平均庫倫效率達0.98。 在碳矽複材方面，將木質纖維素、木質素與回收矽粒子均勻混合並經600 ̊C無氧燒結後，形成兩種不同構型的碳矽複材，分別為矽附著碳與碳包覆矽，而矽附著碳的構型形同於矽粒子裸露於外並無碳層的包覆，因此其循環表現類似於矽電極；而碳包覆矽的構型則有利於增加矽表面的導電網路並有助於形成穩定SEI膜及緩衝矽粒子膨脹的能力，而木質素與矽所合成的碳矽複材，其電極平均嵌出電容量為1411.4 mAh/g C-Si+KS-6，循環51圈後電容量保留率高達79.1 %。; The negative electrodes of lithium-ion batteries prepared in this study were composed of kerf-loss silicon slurries and by-products recovered from photovoltaic and pulp industries, respectively. Although the theoretical capacity of silicon is about ten times of graphite, the lithiation mechanism (alloying) leads to dramatic volume expansion which brings about detrimental effects on cycling stability such as silicon particle pulverization, electrical contact loss and rupture of the SEI layer. In order to overcome these drawbacks, we employed two methods to improve the cycling performance of silicon electrode: (i) searching for a binder that possesses better adhesion to electrode materials and the copper foil, and utilizes capacity of active materials effectively; (ii) fabricating carbon-silicon composites by employing carbon precursor (lignin, lignocellulose) to coat a carbon layer on silicon surface for enhancing electric conductivity of silicon and forming stable SEI layers. We mainly used poly(acrylic acid) or alginic acid sodium salt as a binder and some were combined with emulsified styrene butadiene rubber. The experiment result showed that the silicon electrode using poly(acrylic acid) as a binder has the best capacity performance. The lithiation and delithiation capacities of the first cycle are 2738.8 and 2287.8 mAh/g Si+KS-6 with the coulombic efficiency of 83.5 %, and the irreversible capacity is only 451 mAh/g Si+KS-6. Our research reported that when the ratio of silicon, KS-6 and PAA is 3:6:1, the silicon electrode has a much better cycling performance which delivers average delithiation capacity of 1025.9 mAh/g Si+KS6 over 51 cycles with average coulombic efficiency of 98 % and capacity retention of 70.0 %. For carbon-silicon composites, there is a significant difference between these two composite structures (lignocellulose/Si, lignin/Si) which forms silicon-coated carbon and carbon-coated silicon, respectively. The latter configuration which silicon particle is coated with an amorphous carbon layer by pyrolization of lignin is beneficial to enhance the conductive network, form a stable SEI layer and buffer the volume change of silicon. The electrode of lignin-based carbon-coated silicon composite exhibits average delithiation capacity of 1411.4 mAh/g C-Si+KS6 with 79.1 % capacity retention after 51 cycles. Mon, 01 Jan 2018 00:00:00 GMT http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/71091 2018-01-01T00:00:00Z http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/18518 標題: 黃銅礦結構薄膜太陽電池光吸收層與緩衝層材料之製備與特性分析; Preparation and Characterization of Chalcopyrite-based Films Used in the Absorber Layers and Buffer Layers of Thin-film Solar Cells 作者: Shin-Hom Lin; 林信宏 摘要: 本論文針對黃銅礦結構太陽電池緩衝層材料及光吸收層材料進行製備與特性分析。利用塗佈法結合硒化製程製備黃銅礦結構之ZnIn2Se4薄膜，並做為替代型緩衝層薄膜應用於Cu(In,Ga)Se2太陽電池。為改善薄膜之晶粒成長與光電特性，利用鉍成份來添加進入濺鍍法製備之Cu(In,Ga)Se2薄膜中。並為提昇吸收層薄膜之表面能隙及減少硒缺陷，使用硫成份來導入吸收層薄膜Cu(In,Ga)(Se,S)2之表面以提昇其薄膜之光電特性。為進一步提昇光電特性與減少薄膜內部缺陷，Cu(In,Ga)(Se,S)2薄膜將以改質式硒硫化反應來製備，並針對於本研究中所製備之太陽光電元件特性與理想因子分析之影響進行探討 論文第一部份使用塗佈法結合硒化法成功製備黃銅礦結構之ZnIn2Se4薄膜。隨增加硒化反應溫度，所製備得之ZnIn2Se4薄膜的緻密程度與導電特性可以被增加。並利用ZnIn2Se4薄膜作為緩衝層結合Cu(In,Ga)(Se,S)2薄膜製作太陽光電元件，可有效產生光電流。以塗佈法結合硒化法成功製備之ZnIn2Se4薄膜，可製作為替代式緩衝層薄膜於CIGS太陽電池之應用中。 本論文之第二部份中，為提昇Cu(In,Ga)Se2太陽電池之光電特性，開發利用鉍添加入濺鍍法製備Cu(In,Ga)Se2薄膜之中。添加入鉍於硒化過程中可形成銅鉍硒化合物與前驅膜產生液相燒結，並可提昇整體薄膜之晶粒成長與緻密程度。於鉍添加之Cu(In,Ga)Se2薄膜可提昇鎵離子擴散並改善晶粒成長特性，其所製備Cu(In,Ga)Se2太陽電池之光電轉化效率可有效提升。 於第三部份中，以硒化法結合後硫化法製備Cu(In,Ga)(Se,S)2薄膜。於硒化法結合硫化法後，可於吸收層薄膜表面形成高硫含量之Cu(In,Ga)(Se,S)2薄膜，並提昇吸收層與緩衝層接面的能隙。並於螢光光譜分析中指出經由後硫化反應之適化控制可有效減少薄膜表面之硒缺陷。經由後硫化反應處理後，Cu(In,Ga)(Se,S)2太陽電池之開環電壓、填充因子及轉化效率可進一步提昇。 於論文之第四部份，以改良式硒硫化製程製備Cu(In,Ga)(Se,S)2薄膜並進行分析研究。於此改良式硒硫化製程反應後，薄膜中之鎵離子擴散可被提昇並其薄膜中之電子電洞再結合可被有效抑制。於本部份中所製備之Cu(In,Ga)(Se,S)2薄膜之光電轉化效率、開環電壓及填充因子可被有效增加。在最後部份中，在以鉍成份添加進入改質式硒硫化製程製備之Cu(In,Ga)(Se,S)2薄膜中，其薄膜所組成之太陽光電元件效率進一步提昇。本研究成功開發黃銅礦緩衝層薄膜之與製備具有高效率之Cu(In,Ga)(Se,S)2太陽電池，可用於提昇黃銅礦結構之太陽電池特性與發展應用。; The chalcopyrite-based buffer and absorber layers were prepared for the application of Cu(In,Ga)Se2-based solar cells in this thesis. Zinc indium selenide films with a defective chalcopyrite structure were fabricated via a spin coating route for the alternative buffer layers used in Cu(In,Ga)Se2-based solar cells. The bismuth species were added into sputtering-derived Cu(In,Ga)Se2 films to improve the grain growth and the photovoltaic properties of the obtained films. Additionally, the sulfur species were incorporated into Cu(In,Ga)Se2 films for increasing the band gap and reducing the defects of selenium near the surface region of absorber films. For further increasing the photovoltaic characteristics and eliminating the defects of solar cells, Cu(In,Ga)(Se,S)2 films were prepared via the modified selenization and sulfurization process. The photovoltaic performance and diode analysis of the fabricated solar cells were investigated. Defective chalcopyrite-based ZnIn2Se4 films were successfully synthesized via a spin coating process with a sequential selenization treatment. With elevating the selenziation temperature, the densification and electric properties of the prepared ZnIn2Se4 films were significantly increased. The photocurrent was generated from the Cu(In,Ga)Se2 films combined with the spin-coated ZnIn2Se4 films. ZnIn2Se4 layers prepared via the spin coating process were presented to be an effective approach for the alternative buffer layers used in Cu(In,Ga)Se2 solar cells. In the second section, for increasing the photovoltaic properties of Cu(In,Ga)Se2 films, bismuth species were utilized to add into sputtering-derived Cu(In,Ga)Se2 films. The liquid-phase sintering was yielded by copper bismuth selenide compound to facilitate the grain growth and densification of obtained Cu(In,Ga)Se2 films. The conversion efficiency of the bismuth-doped Cu(In,Ga)Se2 solar cells was effective increased owing to the improvement of the gallium distribution and the grain growth resulted from the bismuth-ion doping. In the third section, the preparation for Cu(In,Ga)(Se,S)2 films incorporated with sulfur species via a sulfurization treatment after selenization process was investigated. The Cu(In,Ga)(Se,S)2 layers with sulfur-rich content were formed near the surface region of absorber films to increase the band gap at the interface of absorber/buffer layers. The photoluminescence spectra indicated that the selenium vacancies near the surface region of the obtained Cu(In,Ga)(Se,S)2 films were significantly reduced with the well-controlled duration of sulfurization. The conversion efficiency of the resulting Cu(In,Ga)(Se,S)2 solar cells were further increased owing to the improvement of open circuit voltage and fill factor. In the four section, Cu(In,Ga)(Se,S)2 films were prepared using the modified chalcogenization process. After the reaction of the modified chalcogenization method, the gallium distribution of the prepared Cu(In,Ga)(Se,S)2 films could be improved and the recombination of electron and hole in obtained absorber films was further suppressed. The conversion efficiency of the fabricated solar cells using the Cu(In,Ga)(Se,S)2 films derived from the modified chalcogenization process was improved. Moreover, the photovoltaic performance of the bismuth-doped Cu(In,Ga)(Se,S)2 absorber films with via the modified chalcogenization method was further improved by the well controlling of doping with bismuth and sulfur species. This thesis developed the new preparation process for the alternative buffer layers and fabricating highly-efficient Cu(In,Ga)(Se,S)2 solar cells used in the field of CIGS-based photovoltaic technology. Wed, 01 Jan 2014 00:00:00 GMT http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/18518 2014-01-01T00:00:00Z http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/1207 標題: 鹽類價數與奈米通道之幾何形狀對其整流行為的影響; Influences of Salt Valence and Geometric Shape of a Nanochannel on Its Rectification Behavior 作者: Yu-Min Chen; 陳俞閔 摘要: 在奈米流體尺度下，電雙層重疊效應顯著，使奈米通道可引起許多有趣的電動力學現象，如離子濃度極化(ICP)和離子電流整流(ICR)，也因而製備與合成奈米通道成為奈米科技上的一股熱潮。在第一章節中，我們利用數值模擬的方法，考慮不同電解質溶液LaCl3、CaCl2、KCl、KNO3、K2SO4，研究其離子價數比之不對稱性對圓錐形奈米通道的離子整流效應所造成的影響。改變價數比時有兩種方式，第一種方式是固定陰離子的價數，改變陽離子的價數;而第二種則是固定陽離子的價數，改變陰離子的價數。我們發現，離子強度與離子擴散係數對其電動力學現象扮演著舉足輕重的角色。另外，定性上帶正電的奈米通道之整流行為與帶負電的奈米通道相似。第二章節中，我們則是討論一表面具有pH可調節電荷之兩性離子基團的仿生雪茄形奈米通道。考慮在外加電場作用下，溶液酸鹼值pH、溶液鹽濃度、底端的開口半徑以及奈米通道形狀對離子傳輸行為的影響。藉由調節孔口半徑與表面曲率以得到雪茄形奈米通道的最佳整流表現與離子選擇性。除了能夠解釋相關電動力學現象之外，所獲得的結果還為相關設備的複雜設計提供了必要的資訊。; The overlapping of electric double layer in a nano-scaled system is usually significant, rendering it having profound and interesting electrokinetic phenomena, such as ion concentration polarization (ICP) and ion current rectification (ICR), and thus fabrication of nanodevices becomes a trend of nanotechnology. In Chapter 1, by taking account of various electrolyte solution LaCl3、CaCl2、KCl、KNO3, and K2SO4, a thorough numerical simulation is conducted to illustrate the influence of asymmetry of various ionic valence ratio on the ICR behavior in a conical nanochannel. We show that the electrokinetic phenomena depend highly on ionic strength and ion diffusivity. The qualitative behavior of the ion current rectification of a positively charged conical nanochannel is similar to that of a negatively charged one.In Chapter 2, we consider a bioinspired cigar-shaped nanochannel where its surface is pH-regulated, and has zwitterionic groups. The influences of the solution pH, the bulk concentration, the base opening radii, and the nanochannel shape on the associated ICR behavior and ionic selectivity are examined, focusing on discussing the underlying mechanisms in detail. We show that the best nanochannel performance can be achieved by adjusting the base orifice radii and surface curvature appropriately. In addition to proposing underlying mechanisms for the phenomena observed, the results gathered in this study also provide necessary information for designing relevant devices. Mon, 01 Jan 2018 00:00:00 GMT http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/1207 2018-01-01T00:00:00Z http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/93726 標題: 鹽濃差度梯度產生的滲透能：孔道表面波形設計的影響及修正後的電動模型對離子尺寸和介電效應的研究; Osmotic Power from Salinity Gradient: Impact of Surface Waveform Design and a Modified Electrokinetic Model Investigating Ion Size and Dielectric Effects 作者: 劉仲崴; Chung-Wei Liu 摘要: 近年來，學術研究對於鹽濃差發電的興趣日益增長，這種創新方法利用鹽水和淡水間的鹽度差異，讓離子通過奈米孔道時產生電力。先前的理論研究主要集中在內表面光滑的奈米孔道上。從鹽度梯度中成功提取滲透壓能源的關鍵在於奈米孔道的離子選擇性能。這要求奈米孔道材料與水溶液接觸的表面具有適當的表面電荷，並且奈米孔的尺寸應當與電雙層的尺寸匹配。 第一章中，為了提升奈米流體滲透壓發電的性能，我們研究了四種具有獨特波形內表面設計（方形、鋸齒形、三角形和正弦波）的圓柱形奈米孔道。此研究聚焦於探討系統濃度效應和固液界面幾何特性對發電表現的影響。我們證明了波形孔道內表面的存在引入了新的變數，這些變數對奈米流體系統的整體性能產生重大影響。在波形孔道內表面的最佳振幅下，提高波形頻率顯著改善了滲透電流、擴散電位、最大功率和最大效率。這些研究成果已經發表在Physical Chemistry Chemical Physics journal上。 然而，目前的研究主要依賴標準的泊松-能斯特-普朗克（Poisson-Nernst-Planck, PNP）模型，該模型過於簡化離子為點電荷，並忽略了如離子的有限大小、波恩能（Born energy）和介電能等關鍵因素。在第二章中，為了修正這些遺漏，我們採用了一種將溶液介電常數視為濃度函數的觀點，並為每種離子引入了修改後的化學勢能，從而提出了一種修改後的PNP模型。該模型全面考慮了離子的體積效應、波恩力和介電力。我們的研究旨在描述標準PNP模型和修改後PNP模型之間的差異，包括系統性能如電流、擴散電位、最大功率和最大效率等方面。通過這一探討，我們提供了電動力學現象的新見解，揭示了由奈米孔內離子分佈引發的現象。; In recent scholarly inquiries, there has been a growing interest in salinity gradient power, an innovative method exploiting the disparity in salinity between brine and fresh water to generate electricity via nanopores. Previous theoretical studies in this field based mainly on nanopores having a smooth inner surface. The successful operation of osmotic power derived from salinity gradients hinges on the ion-selective properties of the nanopore. This necessitates that the surface of the nanofluidic material in contact with the salt solution carries an appropriate charge, and that the dimensions of the nanofluidic channels align with those of the electrical double layer (EDL). In Chapter 1, to enhance the performance of nanofluidic osmotic power, we investigated four types of cylindrical nanopore, each has a unique waveform wall design (square, sawtooth, triangle, and sine waves). This study focused on elucidating the influence of bulk salt concentration and geometric characteristics at the solid-liquid interface. We demonstrated that the presence of a waveform wall introduces new variables that have a significant impact on the overall performance of a nanofluidic osmotic power system. At the optimal amplitude of the waveform wall, raising waveform frequency can improve remarkably the osmotic current, diffusion potential, maximum power, and maximum efficiency. These research findings have been published in the Physical Chemistry Chemical Physics journal. However, prevalent studies predominantly rely on the standard Poisson-Nernst-Planck (PNP) model, which oversimplifies ions as point charges and neglects crucial factors such as the finite size of ions, Born energy and dielectric energy differences. In Chapter 2, to rectify these oversights, we adopt a perspective that considers solution permittivity as a concentration-dependent function and introduce a modified chemical potential for each ionic species, leading to the formulation of a modified PNP model. This model comprehensively accounts for ion steric effects, Born, and dielectric forces. Our investigation aims to delineate disparities between standard and modified PNP models, encompassing system performance such as current, diffusion potential, maximum power, and maximum efficiency. Through this rigorous examination, we offer novel insights into the electrokinetic phenomenon, shedding light on profound phenomena arising from ion distribution within nanopores. Mon, 01 Jan 2024 00:00:00 GMT http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/93726 2024-01-01T00:00:00Z