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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 藍崇文(Chung-Wen Lan) | |
| dc.contributor.author | Chuan-Wei Liu | en |
| dc.contributor.author | 劉洤瑋 | zh_TW |
| dc.date.accessioned | 2023-03-19T23:41:25Z | - |
| dc.date.copyright | 2022-09-05 | |
| dc.date.issued | 2022 | |
| dc.date.submitted | 2022-09-02 | |
| dc.identifier.citation | [1] Wertheim, G. K., Van Attekum, P. T. M., & Basu, S. (1980). Electronic structure of lithium graphite. Solid State Communications, 33(11), 1127-1130. doi:10.1016/0038-1098(80)91089-3. [2] Su, X., Wu, Q., Li, J., Xiao, X., Lott, A., Lu, W., ... & Wu, J. (2014). Silicon‐based nanomaterials for lithium‐ion batteries: a review. Advanced Energy Materials, 4(1), 1300882. doi: 10.1002/aenm.201300882 [3] An, Y., Tian, Y., Wei, C., Zhang, Y., Xiong, S., Feng, J., & Qian, Y. (2020). Recent advances and perspectives of 2D silicon: synthesis and application for energy storage and conversion. Energy Storage Materials, 32, 115-150., doi:10.1016/j.ensm.2020.07.006. [4] Lu, Z., Zhu, J., Sim, D., Zhou, W., Shi, W., Hng, H. H., & Yan, Q. (2011). Synthesis of ultrathin silicon nanosheets by using graphene oxide as template. Chemistry of Materials, 23(24), 5293-5295, doi: 10.1007/s11434-012-5252-6 [5] Kim, W. S., Hwa, Y., Shin, J. H., Yang, M., Sohn, H. J., & Hong, S. H. (2014). Scalable synthesis of silicon nanosheets from sand as an anode for Li-ion batteries. Nanoscale, 6(8), 4297-4302. doi: 10.1039/c3nr05354g. [6] Zhang, W., Sun, L., Nsanzimana, J. M. V., & Wang, X. (2018). Lithiation/delithiation synthesis of few layer silicene nanosheets for rechargeable Li–O2 batteries. Advanced Materials, 30(15), 1705523. doi: 10.1002/adma.201705523 [7] Huang, X., Cen, D., Wei, R., Fan, H., & Bao, Z. (2019). Synthesis of porous Si/C composite nanosheets from vermiculite with a hierarchical structure as a high-performance anode for lithium-ion battery. ACS applied materials & interfaces, 11(30), 26854-26862. doi: 10.1021/acsami.9b06976. [8] Loaiza, L. C., Monconduit, L., & Seznec, V. (2019). Siloxene: A potential layered silicon intercalation anode for Na, Li and K ion batteries. Journal of Power Sources, 417, 99-107. doi:10.1016/j.jpowsour.2019.02.030. [9] Fu, R., Zhang, K., Zaccaria, R. P., Huang, H., Xia, Y., & Liu, Z. (2017). Two-dimensional silicon suboxides nanostructures with Si nanodomains confined in amorphous SiO2 derived from siloxene as high performance anode for Li-ion batteries. Nano Energy, 39, 546-553., doi:10.1016/j.nanoen.2017.07.040. [10] Zhao, J., Liu, H., Yu, Z., Quhe, R., Zhou, S., Wang, Y., ... & Wu, K. (2016). Rise of silicene: A competitive 2D material. Progress in Materials Science, 83, 24-151.,doi:10.1016/j.pmatsci.2016.04.001. [11] Ryan, B. J., Hanrahan, M. P., Wang, Y., Ramesh, U., Nyamekye, C. K., Nelson, R. D., ... & Panthani, M. G. (2019). Silicene, siloxene, or silicane? Revealing the structure and optical properties of silicon nanosheets derived from calcium disilicide. Chemistry of Materials, 32(2), 795-804. doi:10.1021/acs.chemmater.9b04180. [12] Gao, R., Tang, J., Terabe, K., Yu, X., Sasaki, T., Hashimoto, A., ... & Nakura, K. (2019). Preparation of layered Si materials as anode for lithium-ion batteries. Chemical Physics Letters, 730, 198-205, doi:10.1016/j.cplett.2019.06.010. [13] Sugiyama, Y., Okamoto, H., & Nakano, H. (2010). Synthesis of siloxene derivatives with organic groups. Chemistry letters, 39(9), 938-939, doi:10.1246/cl.2010.938. [14] Zheng, X., Cong, H., Yang, T., Ji, K., Wang, C., & Chen, M. (2022). High-efficiency 2D nanosheet exfoliation by a solid suspension-improving method. Nanotechnology, 33(18), 185602.. doi: 10.1088/1361-6528/ac4b7c. [15] Huang, X., & Wu, P. (2020). A facile, high‐yield, and freeze‐and‐thaw‐assisted approach to fabricate MXene with plentiful wrinkles and its application in on‐chip micro‐supercapacitors. Advanced Functional Materials, 30(12), 1910048.doi:10.1002/adfm.201910048 [16] Cai, M., Thorpe, D., Adamson, D. H., & Schniepp, H. C. (2012). Methods of graphite exfoliation. Journal of Materials Chemistry, 22(48), 24992-25002, doi:10.1039/C2JM34517J. [17] Lin, H., Qiu, W., Liu, J., Yu, L., Gao, S., Yao, H., ... & Shi, J. (2019). Silicene: wet‐chemical exfoliation synthesis and biodegradable tumor nanomedicine. Advanced Materials. doi:10.1002/adma.201903013 [18] Nakano, H., Ishii, M., & Nakamura, H. (2005). Preparation and structure of novel siloxene nanosheets. Chemical communications, (23), 2945-2947, doi:10.1039/b500758e. [19] Gonzalez-Rodriguez, R., del Castillo, R. M., Hathaway, E., Lin, Y., Coffer, J. L., & Cui, J. (2022). Silicene/Silicene Oxide Nanosheets for Broadband Photodetectors. ACS Applied Nano Materials, 5(3), 4325-4335, doi:10.1021/acsanm.2c00337. [20] Nakano, H., Mitsuoka, T., Harada, M., Horibuchi, K., Nozaki, H., Takahashi, N., ... & Nakamura, H. (2006). Soft synthesis of single‐crystal silicon monolayer sheets. Angewandte Chemie International Edition, 45(38), 6303-6306.doi:10.1002/anie.200600321 [21] Yin, S., Ji, Q., Zuo, X., Xie, S., Fang, K., Xia, Y., ... & Cheng, Y. J. (2018). Silicon lithium-ion battery anode with enhanced performance: Multiple effects of silver nanoparticles. Journal of materials science & technology, 34(10), 1902-1911, doi:10.1016/j.jmst.2018.02.004. | |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/86192 | - |
| dc.description.abstract | 隨著近年來電動車的崛起，鋰電池產業研究也變成最熱門的研究之一。而矽作為擁有石墨10倍以上的電容，被認為會成為下一世代鋰離子電池的負極材料，但矽在充放電過程中體積膨脹劇烈的問題仍需要解決。而二維結構的矽可以有效解決此問題，由於二維結構膨脹僅有厚度方向的上下膨脹，因此體積膨脹能降低一半以上。文獻中有多種合成二維矽的方法，其中矽化鈣的拓樸反應為一種簡單、低成本的方式，文獻中多使用低溫鹽酸水溶液的方式去合成低含氧的堆疊分層矽烯片，再透過震盪的方式去進行剝離來產生奈米矽烯片，最後經過鍛燒成為奈米片狀矽。雖說擁有好的形貌，但在長時間水溶劑反應下會造成氧化，導致電池表現變差，且大多論文多沒提及其產率，或提到產率小於3%[19]，也沒人將奈米矽烯片應用於鋰電池領域中。 在此研究中，吾人先嘗試在不同水與乙醇的溶劑比例中，發現在純乙醇的溶劑下可以獲得最佳可剝離的形貌，取代文獻中所使用的低溫水溶劑。並發現在純乙醇下不同反應溫度，剝離後所獲得的片狀擁有不同的尺寸與厚度，另外吾人也發現到在不同起始固含量進行剝離所得到的產率有所不同，在低固含量剝離時甚至可達到10%，遠高於文獻中所提及的3%[19]。於無水乙醇溶劑中反應，最大的優勢在於即使反應時間拉長，由於沒有氧源，不會造成矽烯片的氧化，能得到良好形貌及低氧化的矽烯片。最後吾人將奈米矽片應用於鋰離子電池中，能夠得到1980 mA h/g的起始電容、59.8%首圈效率、並在250圈後仍有810 mA h/g的可逆電容、96.6%的電容保持率等良好循環性的表現，期望能應用於未來鋰電池市場之中。 | zh_TW |
| dc.description.abstract | Silicon, as a capacity with more than 10 times that of graphite, is considered to be the anode material for the next generation of lithium-ion batteries, but the problem of severe volume expansion of silicon during charging and discharging still needs to be solved. The two-dimensional structure of silicon can effectively solve this problem. There are many methods for synthesizing 2D silicon in the literature. Among them, the topological reaction of calcium silicide is a simple and low-cost method. In the literature, low-temperature hydrochloric acid aqueous solution is often used to synthesize low-oxygen multi-layer silicene. The silicene nanosheet is produced by exfoliation by sonication. Although it has a good morphology, it has not mentioned its yield, or mentioned that the yield is less than 3%[19], and no one has applied silicene nanosheets in the field of lithium batteries. In this study, we first tried in different solvent ratios of water and ethanol, and found that the best morphology can be obtained in anhydrous ethanol solvent, replacing the low-temperature water solvent used in the literature. It was found that under different reaction temperatures in anhydrous ethanol, the sheets obtained after exfoliation had different diameters and thicknesses. In addition, we also found that the exfoliation yields at different initial solid contents were different. It can even reach 10% at low solid content, which is much higher than the 3% mentioned in the literature.[19] Finally, we apply silicene nanosheets to lithium-ion batteries, which can achieve high capacitance and good cycle performance, and hope to be applied to the future lithium battery market. | en |
| dc.description.provenance | Made available in DSpace on 2023-03-19T23:41:25Z (GMT). No. of bitstreams: 1 U0001-0109202223150000.pdf: 4201587 bytes, checksum: b4870dba55fbd20e033a8b97706dc9e0 (MD5) Previous issue date: 2022 | en |
| dc.description.tableofcontents | 目錄 致謝 I 中文摘要 II Abstract III 圖目錄 V 表目錄 XI 第一章 緒論 1 第二章 文獻回顧 3 2-1 二維矽合成 3 2-2 拓樸反應合成堆疊分層片狀矽 8 2-3 剝離片狀矽方法 14 2-4 研究動機 18 第三章 實驗方法及實驗器材 19 3-1 實驗藥品 19 3-2 實驗設備與器材 21 3-3 實驗設計 25 第四章 研究結果及討論 30 4-1 拓樸反應 30 4-2 片狀剝離探討 35 4-3 電性分析 40 第五章 結論 49 參考文獻 50 圖目錄 圖1- 1 The advantages of silicon used in lithium batteries [3]. 1 圖1- 2 The advantages of two dimensional silicon used in lithium batteries [3]. 2 圖2- 1 The evolution of fabrication stragies of two dimensional silicon.[3] 3 圖2- 2 Characterization of silicon nanosheets synthesized using GO as temple. (a) schematic illustration of the synthesis of 2D Si from a GO template. (b) 4 μm silicon nanosheets. (c) Cyclic performance of as-obtained Si nanosheets and Si nanoparticles anodes for LIBs.[4] 4 圖2- 3 Characterization and performance of 2D silicon synthesized by magnesiothermic reduction from natural sand. (a) Scheme of fabrication of 2D silicon nanosheets and RGO encapsulated silicon nanosheets. (b) SEM image of 2D silicon nanosheets. (c) Cyclic performance of commercial nano-silicon, 2D silicon nanosheets and RGO encapsulated silicon nanosheets. [5] 5 圖2- 4 Characterization and performance of 2D silicene nanosheets synthesized by lithiation/delithiation process from bulk silicon precursor.(a) Schematic illustrating of lithiation and delithiation processes of silicon at various scenarios. (b) 4 μm silicon nanosheets. (c) Voltage curves of various electrodes. [6] 6 圖2- 5 Characterization and performance of porous silicon/carbon nanosheets synthesized by aluminothermic reduction method from vermiculite precursor. (a) Schematic illustrating of fabrication. (b) SEM image of expanded vermiculite. (c) SEM image of silicon/carbon nanosheets. (d) Long-term cyclic performance of silicon/carbon anode for LIBs. [7] 7 圖2- 6 (a) Illustration of calcium disilicide structure. [8] (b) SEM image of calcium disilicide. [9] 8 圖2- 7 (a) Illustration of calcium disilicide structure. [8] (b) SEM image of calcium disilicide. [9] (c) Illustration[8] and (d) SEM image[9] of siloxene. (d) Illustration[10] and (d) SEM image[11] of silicene. 9 圖2- 8 (a) Structure of as-prepared siloxene. (b) Schematic illustration of nano-Si/a-SiO2@C composites. (c) TEM images of partial delaminated sheet-like nano-Si/a-SiO2@C. (d) Galvanostatic charge/discharge profiles of nano-Si/a-SiO2@C electrode upon different cycles at 0.15 A g−1. (e) Comparison of the nano-Si/a-SiO2@C cycling performance for 33.4 and 44.7 wt% carbon content at 0.75 A g−1 after the first two activating cycles are ran at 0.15 A g−1.[9] 10 圖2- 9 (a) Illustration of the transformation of CaSi2 into Siloxene upon reaction with HCl. (b) SEM images of siloxene. (c) Galvanostatic curves for the first cycle and (d) cycling performance of siloxene.[8] 11 圖2- 10 (a) Schematic illustration of the synthesis process of LSM, (b) top view of model structure. SEM images of (c) LSM at low magnification, (d) LSM at high magnification. (e) Voltage profiles for the initial two cycles at 1000 mA g−1. (f) Cycling performances of LSM cycled in the potential range of 0.005–3 V.[12] 12 圖2- 11 (a) The structure of the reaction of CaSi2 with hydrogen chloride in alcohol., (b) IR spectra of organosiloxene (a:Si6H5(OBu),b:Si6H5(OC12H25),c:Si6H5(O C6H5CH2), and d: Si6H5(OCH2COOMe)) (c) SEM image of organosiloxene.[13] 13 圖2- 12 Synthesis and characterization of 2D silicene nanosheets. (a) Scheme for the synthesis of 2D silicene nanosheets. (b) Schematic diagram of silicene nanosheet exfoliation process including mild oxidation and ultrasound delamination. (c) SEM images and (d) HR-STEM image of pristine CaSi2. SEM images of multilayer silicene. Scale bars, (e) 1 µm ;(f) 50 nm. (g) Bright-field and (h) dark-field TEM image of few- or single-layered silicene nanosheets. Scale bars, 100 nm.[17] 15 圖2- 13 (a) Scheme for the synthesis of 2D silicene nanosheets by SDS. (b) TEM image of siloxene nanosheets. (c) Tapping mode AFM image of siloxene nanosheets. [18] 16 圖2- 14 (a) Diagram for the fabrication of silicene/silicene oxide layers from CaSi2. SEM images of (b) CaSi2, (c) ML silicene/silicene oxide, and (d) few-layer silicene/silicene oxide layers. TEM images of (e and h) CaSi2, (f and i) ML silicene/silicene oxide, and (g and j) few- or single-layer silicene/silicene oxide. [19] 17 圖3- 1 Schematic illustrating of synthesis process of silicon nanosheets 25 圖3- 2 Setup of topochemical reaction (a) schematic diagram, (b) picture and (c) picture of silicene start to change color. 26 圖3- 3 The process of exfoliation. (a) Silicene after topochmical reaction. (b) Suspension and precipitate of silicene. (c) Positive pressure filtraction. (d) Silicene sheet paper. (e) Centrifugation. (f) Silicene nanosheets after exfoliation. (g) Tube furnace. (h) Spray coating setup. 28 圖3- 4 (a) Schematic illustration and (b) picture of spray coating. (c) Spray coating electrode. 29 圖4-1 XRD spectra of CaSi2 and silicene with different solvent ratios 31 圖4-2 SEM images of (a) raw-CaSi2 and multilayer silicene nanosheets from (b) HCl solution, (c) 95% ethanol,(d) anhydrous ethanol at 35°C. 32 圖4-3 SEM images of multilayer silicene from anhydrous ethanol at (a) -20°C,(b) 0°C, (c) 35°C and (d) 70°C . 33 圖4-4 XRD spectra of CaSi2 and silicene at different reaction temperatures in anhydrous ethanol. 34 圖4-5 (a-e) Evolution of silicene at 0°C in anhydrous ethanol. 35 圖4-6 SEM images of silicene at 0°C in anhydrous ethanol (a) before exfoliation, after exfoliation nanosheets (b) collected by centrifugation ,(c,d) collected by positive pressure filtration and (e) optical image of silicene sheet paper. 36 圖4-7 Line graph of (a) repeated ultrasonic yields and (b) yields and solids content of suspensions at different initial solids contents. 37 圖4-8 Schematic diagram of the setup for continuous exfoliation of silicene nanosheets. 38 圖4-9 SEM images of silicene nanosheets (a) at -20°C in water solvent and (b,c,d) at 0°C ,35°C,70°C in anhydrous ethanol. Optical images of silicene sheet papers at (e) 0°C and (f) 70°C in anhydrous ethanol. 39 圖4-10 Schematic illustrating of spray coating. 40 圖4-11 SEM images of spray coating electrode. Top view with different magnifications (a) 1000 x ,(b) 20000 x , cross section. Cross section of different thickness. (c) 2μm (d) 9.67 μm 41 圖4-12 Cyclic voltammetry curves of silicon nanosheets at a scanning rate of 0.1 mV /s, and voltage range between 0.01 V and 2.7 V vs. Li+/Li for the first 2 cycles. 42 圖4-13 (a) 1st charge/discharge curves of Si nanosheets synthesized at -20°C in water solvent and at 0°C,35°C,70°C in anhydrous ethanol solvent. (b) 1st discharge capacity and initial coulombic efficiency of Si nanosheets synthesized at -20°C in water solvent and at 0°C,35°C,70°C in anhydrous ethanol solvent. 43 圖4-14 Cycling performance and coulombic efficiency of Si nanosheets. (Current density: 0.1 A/g for first cycles; 1 A/g between 2~9 cycles ; 2 A/g after 10 cycles) 44 圖4-15 Rate capability of silicon nanosheests. (Current density at 0.1 ~5.0 A/g). 45 圖4-16 a) Cycling performances of Si nanosheets at different mass loading. (b) Cycling performances of spherical SiOx. at different mass loading.[22] 46 圖4-17 SEM images of electrode before and after 200 cycles. (a) Top view ,(b) cross section before cycle. (a) Top view ,(b) cross section after 200 cycle. 47 表目錄 表3- 1 Composition of solvent with different solvent ratios 26 表3- 2 Chemical compounds used in topochemical reaction. 27 表4- 1 EDS analysis of silicene at -20°C in anhydrous ethanol 33 | |
| dc.language.iso | zh-TW | |
| dc.subject | 二維矽 | zh_TW |
| dc.subject | 奈米片 | zh_TW |
| dc.subject | 負極材料 | zh_TW |
| dc.subject | 鋰離子電池 | zh_TW |
| dc.subject | 矽化鈣 | zh_TW |
| dc.subject | 矽烯 | zh_TW |
| dc.subject | nanosheets | en |
| dc.subject | lithium-ion batteries | en |
| dc.subject | anode | en |
| dc.subject | silicene | en |
| dc.subject | 2D silicon | en |
| dc.subject | calcium silicide | en |
| dc.title | 從二矽化鈣合成片狀矽在鋰電池負極的應用 | zh_TW |
| dc.title | Synthesis of Silicon Nanosheets from Calcium Silicide as Anode for Lithium-ion Batteries | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 110-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 王大銘(Da-Ming Wang),陳嘉晉(Chia-Chin Chen) | |
| dc.subject.keyword | 矽化鈣,奈米片,二維矽,矽烯,負極材料,鋰離子電池, | zh_TW |
| dc.subject.keyword | calcium silicide,nanosheets,2D silicon,silicene,anode,lithium-ion batteries, | en |
| dc.relation.page | 52 | |
| dc.identifier.doi | 10.6342/NTU202203088 | |
| dc.rights.note | 同意授權(全球公開) | |
| dc.date.accepted | 2022-09-02 | |
| dc.contributor.author-college | 工學院 | zh_TW |
| dc.contributor.author-dept | 化學工程學研究所 | zh_TW |
| dc.date.embargo-lift | 2022-09-05 | - |
| 顯示於系所單位： | 化學工程學系 | |
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