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研究生： 陳益鴻
Chen, Yi-Hong
論文名稱： 石墨烯/奈米碳管混成物增強水泥複合材料之製備與 特性及新型水泥無機聚合物電池之製備 與電化學阻抗譜和放電性能研究
Preparation and Properties of Graphene/Carbon nanotubes hybrid Reinforced cement composites and Novel Cement Geopolymer Batteries with Electrochemical Impedance Spectroscopy and Discharge Performance
指導教授： 馬振基
Ma, Chen-Chi M.
口試委員: 江金龍
Chiang, Chin-Lung
蔡德豪
Tsai, De-Hao
李宗銘
Li, ZhongMing
胡啟章
Hu, Chi-Chang
學位類別： 博士
Doctor
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2019
畢業學年度： 107
語文別： 中文
論文頁數： 210
中文關鍵詞： 水泥 、石墨烯 、電池 、無機聚合物
外文關鍵詞： Cement, Graphene, Batteries, Geopolymer
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    • 本研究旨在探討奈米強化水泥(Nano reinforced cement)複合材料機械性質和無機聚合物(Geopolymer)電化學的特性，研究內容探討混合石墨烯奈米片(Graphene Nanoplatelets, GNPs)/多壁奈米碳管(Multi-walled carbon nanotubes, MWCNTs)和水泥所組成複合材料的製備和性能以及無機聚合物作為固態電解質的性能分析。主要研究分為以下二個部分:

    1. 石墨烯/奈米碳管混成物增強水泥複合材料之製備與特性
    多壁奈米碳管（MWCNTs）和石墨烯奈米片（GNPs）在水泥複合材料中的應用成功取決於它們的分散性能。在本研究中，MWCNTs和GNPs利用表面活性劑聚羧酸酯醚（Polycarboxylate ether, PC）改性。利用一維MWCNTs橋接在相鄰二維的GNPs之間，有效地避免了GNPs的重新堆疊和MWCNTs的聚集，更有效分散在水溶液中。在MWCNTs和GNPs之間產生了優異的協同效應，提升了各種物理和化學性質。GNPs/MWCNTs混成結構改善了水泥複合材料的機械性能（抗壓強度和抗拉強度）和體積穩定性（乾燥收縮）。電子顯微鏡（SEM）圖像清楚地顯示GNPs/MWCNTs混成物適用於水泥複合材料。 GN11-PC（GN11為GNPs：MWCNTs = 1：1）的混成重量比導致最佳抗壓強度，其強度大於單獨添加GNPs或MWCNTs時獲得的抗壓強度。與空白組樣品相比，含有0.05wt％GN11-PC的水泥複合材料的抗壓強度與空白組樣品相比在28天齡期增加了61％，抗拉強度提高了47.1％，而收縮率降低了6.9％。

    2. 新型水泥無機聚合物電池之製備與電化學阻抗譜和放電性能研究
    本研究提出了以無機聚合物為基材的電池，它具有作為固態電池的良好潛力，它擁有室溫下的快速離子傳導，減少的電池洩漏和不易燃的性質。無機聚合物利用鹼激發（10 M KOH）將研磨的粒狀高爐礦渣（Ground granulated blast furnace slag , GGBFS）製備而成，除了快速硬化和高離子電導率之外，還具有與水泥相似的機械性能。過去一些研究上，利用水泥作為固態電解質可產生足夠的且可持續的電力輸出，但工作電壓和放電持久性很低。實驗結果表明，無機聚合物的電池具有比水泥基電池更好的電化學性能並研究無機聚合物的齡期和聚合程度與其產生的功率密度和工作電壓之間的關係。無機聚合物的最小體積電阻在第1天為1.9 Ω而電阻率0.65 kΩ·cm。使用無機聚合物電解質，銅片為陰極和鋁片為陽極研究電池的放電電壓，電流密度和功率密度。在0.13 mAcm-2的恆定電流密度下，工作電壓保持在0.97 V並保持穩定600秒。最大電流密度在0.4V時為1173 μAcm-2，最大功率密度為507 μWcm-2。

    The study focuses on the mechanical properties of nano reinforced cement composites and the electrochemical properties of geopolymers. The research topics of this dissertation are related to the preparation and properties of hybrid graphene (Graphene Nanoplatelets, GNPs) / carbon nanotubes (Multi-walled) and performance of the geopolymers as solid electrolytes. There are two parts in this study:

    1. Preparation and properties of graphene/carbon nanotube hybrid reinforced cement composites

    The success of application of multi-wall carbon nanotubes (MWCNTs) and graphene nanoplatelets (GNPs) in cement composites depend on their dispersion properties. In this study, MWCNTs and GNPs were modified by the surfactant polycarboxylate ether (PC). One-dimensional MWCNTs and two-dimensional GNPs led to the MWCNTs forming a bridge between adjacent GNP sheets, effectively avoiding restacking of GNPs and agglomeration of MWCNTs, which resulted in greater dispersion. An excellent synergetic effect was generated between MWCNTs and GNPs, enhancing various physical and chemical properties. Hybrid GNPs/MWCNTs structures improved the mechanical properties of cement composites (compressive strength and tensile strength) and volume stability (drying shrinkage). Scanning electron microscope (SEM) images clearly showed that hybrid GNPs/MWCNTs were compatible for use in cement composites. The hybrid weight ratio of GN11-PC (GN11 means GNPs:MWCNTs = 1:1) led to optimal compressive strength, greater than that obtained upon addition of GNPs or MWCNTs individually. The compressive strength of the cement composites containing 0.05 wt.% GN11-PC (by weight of cement) aged for 28 days increased by 61% in comparison with the blank sample, and the tensile strength increased by 47.1 %, while shrinkage decreased by 6.9 %.

    2. Preparation and Characterization of Novel Cement Geopolymer Batteries with Electrochemical Impedance Spectroscopy and Discharge Performance

    This research presents a geopolymer-based battery that has good potential as a solid-state battery owing to fast ionic conduction at room temperature, reduced battery leakage, and a non-flammable nature. The geopolymer was synthesized by alkali activation (10 M KOH) of ground granulated blast furnace slag (GGBFS), and has a similar mechanical behavior to cement, in addition to rapid hardening and a high ionic conductivity. Some researchers have used cement as an electrolyte to produce a sufficient, sustainable electrical output, but the operation voltage and discharge life are low. The experimental results showed that the geopolymer-based battery had a better electrochemical performance than cement-based batteries. Relationships between the age and polymerization of the geopolymer and the power density and operating voltage it produced were investigated. The minimum bulk resistance and electrical resistivity of the geopolymer were 1.9 Ω and 0.65 kΩ·cm on day 1, respectivily. The discharge voltage, current density, and power density of the battery was investigated using a geopolymer electrolyte, a copper plate cathode, and an aluminum plate anode. Under a constant current density of 0.13 mAcm-2, the operating voltage was maintained at 0.97 V and remained stable for 600 s. The maximum current density was 1173 μAcm−2 at 0.4 V, and the maximum power density was 507 μWcm-2.
     

    目錄 中文摘要 I Abstract III 謝誌 VI 目錄 X 圖目錄 XIV 表目錄 XX 第一章 緒論 1 1-1 前言 1 1-2 水泥簡介 4 1-2-1 波特蘭水泥之水合特性 9 1-3 爐石簡介 13 1-3-1 爐石化學成分和物理性質 14 1-3-2 爐石粉之水化作用及卜作嵐反應 15 1-3-3 爐石粉對混凝土硬固性質之影響 16 1-4 石墨烯簡介 19 1-4-1 石墨烯特性 21 1-4-2 石墨烯製備 23 1-4-3 化學還原型氧化石墨烯 27 1-4-4 化學還原方式 35 1-5 奈米碳管簡介 41 1-5-1 奈米碳管機械性質 43 1-6 無機聚合物(Geopolymer) 45 1-6-1 無機聚合物之發展 46 1-6-2 無機聚合物之聚合反應機制 46 1-6-3 無機聚合物之結構 54 第二章 文獻回顧 ...57 2-1 奈米材料應用於水泥基材料的物理和化學性質 57 2-2 奈米補強水泥和混凝土複合材料 61 2-2-1 奈米材料機械式分散法 62 2-2-2 物理表面改性分散法 63 2-2-3 化學表面改性分散法 64 2-2-4 水泥複合材料的製備 68 2-3 流動性(Slump flow) 70 2-4 奈米材料對水泥水化影響 73 2-5 奈米增強水泥和混凝土的微觀結構複合材料 78 2-6 硬化水泥複合材料的機械性能 80 2-6-1 奈米二氧化矽 80 2-6-2 奈米碳管 80 2-6-3 奈米碳管/卜作嵐材料 82 2-6-4 氧化石墨烯 84 2-7 水泥電化學特性 85 2-8 水泥與聚羧酸系減水劑作用機理 86 第三章 石墨烯/奈米碳管混成物增強水泥複合材料之製備與特性.. 90 3-1 研究目的 90 3-2 實驗部分 93 3-2-1 實驗藥品 93 3-2-2 實驗儀器設備 97 3-2-3 新拌試驗分析 104 3-2-4 硬固試驗分析 104 3-2-5 精密儀器分析法 106 3-2-6 實驗步驟 107 3-3 結果與討論 111 3-3-1 MWCNTs和GNPs在水溶液中的分散 111 3-3-2 流動性試驗和抗壓強度分析結果的比較 113 3-3-3 具有不同水/灰比（W / C）和碳奈米材料含量的抗壓強度 116 3-3-4 具有不同水/灰比（W / C）和碳奈米材料含量的抗拉強度 120 3-3-5 不同水/灰比（W / C）和碳奈米材料的乾燥收縮 122 3-3-6 表面特徵研究 125 3-4 結論 128 第四章 新型水泥無機聚合物電池之製備與電化學阻抗譜和放電性能研究....................... 130 4-1 研究目的 130 4-2 實驗部分 133 4-2-1 實驗藥品 133 4-2-2 實驗儀器設備 134 4-2-3 水泥(OPC)及無機聚合物(Geopolymer)漿體試驗分析 137 4-2-4 硬固試驗分析 138 4-2-5 實驗步驟 142 4-3 結果與討論 146 4-3-1 凝結時間(Setting time) 146 4-3-2 抗壓強度 147 4-3-3 交流阻抗分析 148 4-3-4 不同齡期的水泥和無機聚合物電池放電性能 153 4-3-5 不同齡期的水泥和無機聚合物電池功率密度測試 159 4-3-6 單位密度及含水量重量損失 161 4-3-7 孔隙率 164 4-4 結論 167 第五章 總結論 169 第六章 參考文獻 178 附錄－作者簡介及發表著作一覽表 209 圖目錄 圖1-1 水泥乾縮造成的裂縫 2 圖1-2 水泥加水後發熱曲線變化圖 11 圖1-3 Graphene is a 2D building material for carbon materials of all other dimensionalities. Graphene can be wrapped up into 0D buckyballs, rolled into 1D nanotubes or stacked into 3D graphite [20]. 20 圖1-4 Simulation scheme of the nanostructures of graphene and graphene oxide nanosheets (top row) and the natural amphiphiles of a cellulose dimer, a tri-alanine peptide, and a palmitic acid (bottom row). Color schemes: brown - carbon, red - oxygen, blue - hydrogen, green - nitrogen[35] 24 圖1-5 Variations of the Lerf-Klinowski model indicating ambiguity regarding the presence (top) or absence (bottom) of carboxylic acids on the periphery of the basal plane of the graphitic platelets of GO[38]. 28 圖1-6 Digital pictures of as-prepared graphite oxide dispersed in water and 13 organic solvents through bath ultrasonication (1 h). Top: dispersions immediately after sonication. Bottom: dispersions 3 weeks after sonication. The yellow color of the o-xylene sample is due to the solvent itself 31 圖1-7 A non-contact mode AFM image of exfoliated GO sheets with three height profiles acquired in different locations [40]. 32 圖1-8 Conductivity of thermally reduced GO as a function of the sp2 carbon fraction [39]. 34 圖1-9 Chemically converted graphene suspensions. a,b, Photographs of 15 mg of graphite oxide (GO) paper in a glass vial (a) and the resultant hydrazinium graphene (HG) dispersion after addition of hydrazine (b). Below each vial is a three-dimensional computer-generated molecular model of GO (carbon in grey, oxygen in red and hydrogen in white) and chemically converted graphene, respectively, suggesting that removal of –OH and –COOH functionalities upon reduction restores a planar structure [42]. 36 圖1-10 Images of an individual chemically converted graphene sheet. a–c, Markers are used to obtain SEM (a) and AFM (b,c) images of the same specimen. d, Height profiles taken along the white, red and blue solid lines in c highlight step heights of 0.6 nm. The frequency distribution (bottom) of all heights collected across the area is bimodal[42]. 37 圖1-11 Optical photographs and mechanical properties of the GO films reduced by different chemical agents. (a) Asassembled GO film. (b) 1 h HI acid-reduced GO film at 100 oC. (c) Stress–strain curve of the GO film and HI acid-reduced GO film. (d–f) Hydrazine vapor-, N2H4‧H2O- and NaBH4-reduced GO films. The scale bar in (d–f) is 5 mm[43]. 40 圖1-12 奈米碳管可分為單壁奈米碳管(SWCNT)及多壁奈米碳管(MWCNTs)[49] 42 圖1-13 奈米碳管為石墨單層沿螺旋向量𝐂𝐡方向捲曲，將兩側虛線無縫接合所得之結構。其結構可由(n,m)明確定義[48]。 43 圖1-14 無機聚合物之前導物及主要聚合結構示意圖 47 圖1-15 完整之聚合結構示意圖[68] 49 圖1-16 Na+離子於鋁矽四面體間示意圖[69] 50 圖1-17 無機聚合作用示意圖 53 圖1-18 波特蘭水泥水化過程與無機聚合物聚合機理示意圖 55 圖1-19 無機聚合物結構單元示意圖 55 圖2-1 Comparison of nanofillers with supplementary cementitious materials and aggregates in concrete. Adapted from Sobolev and Ferrada Gutierrez [78]. 60 圖2-2 Effect of 0.05 wt.% GO for w/c of 0.5 on: (a) Stress–strain curves under compression; (b) Load–displacement curves under flexure [120] 85 圖3-1 Mechanism of the synergistic effect between MWCNTs and GNPs in the cement matrix. 92 圖3-2 拌合機 97 圖3-3 恆溫恆濕機 99 圖3-4 乾縮鑄鐵模 99 圖3-5 立方試體模 100 圖3-6 抗壓試驗機 101 圖3-7 抗拉體模 101 圖3-8 指針式比長計 102 圖3-9 流度台 103 圖3-10 場發射掃描式電子顯微鏡Scanning Electron Microscope 103 圖3-11 Sedimentation testing of MWCNTs, GNPs and GNPs/MWCNTs in aqueous solution. (a) 8 mg MWCNTs; (b) 8 mg MWCNTs/0.16 g PC; (c) 8 mg GNPs; (d) 8 mg GNPs/0.16 g PC; (e) 4 mg GNPs /4 mg MWCNTs; (f) 4 mg GNPs/4 mg MWCNTs/0.16 g PC. 112 圖3-12 SEM images of carbon nanofillers. (a) 0.02 wt% G/0.02 wt% N(x20K); (b) 0.02 wt% G/0.02 wt% N/0.8 wt% PC(x20K). 113 圖3-13 Slump flow test results. 115 圖3-14 Compressive strength of cement composites aged for 28 days. 115 圖3-15 Compressive strength of W/C 0.5 cement composites containing various wt.% of GN11-PC 118 圖3-16 Compressive strength of W/C 0.4 cement composites containing various wt.% of GN11-PC. 119 圖3-17 Compressive strength of W/C 0.5 cement composites containing various wt.% of GN11-PC 119 圖3-18 Tensile strength of W/C 0.5 cement composites containing various wt.% of GN11-PC 121 圖3-19 Tensile strength of W/C 0.4 cement composites containing various wt.% of GN11-PC 121 圖3-20 Tensile strength of W/C 0.35 cement composites containing various wt.% of GN11-PC 122 圖3-21 Dry shrinkage of W/C 0.5 cement composites containing various wt.% of GN11-PC 124 圖3-22 Dry shrinkage of W/C 0.4 cement composites containing various wt.% of GN11-PC 124 圖3-23 Dry shrinkage of W/C 0.35 cement composites containing various wt.% of GN11-PC 125 圖3-24 SEM microphotographs of destructed specimens at the age of 28 days (W/C = 0.5) (a) Blank; (b) 0.2 wt.% N-PC; (C) 0.2 wt.% G-PC; (d) 0.05 wt.% GN11-PC; (e) 0.2 wt.% GN11-PC; (f) 0.5 wt.% GN11-PC. 127 圖4-1 無機聚合物電解質電池組裝示意圖 132 圖4-2 水泥初終凝量測儀 135 圖4-3 交流阻抗分析儀 136 圖4-4 電化學分析儀 136 圖4-5 混凝土四點探針分析儀 137 圖4-6 Experimental specimen for EIS analysis 143 圖4-7 Design of a home-made battery device. 144 圖4-8 Experimental specimen for electrical resistivity analysis. 145 圖4-9 EIS of OPC and GP at different water to binder ratios on day 1. 150 圖4-10 EIS of OPC and GP at different water to binder ratios on day 7. 151 圖4-11 EIS of OPC and GP at different water to binder ratios on day 28. 152 圖4-12 Discharge curves of batteries under different constant current density at day 1. 156 圖4-13 Discharge curves of batteries under different constant current density at day 7 157 圖4-14 Discharge curves of batteries under different constant current density at day 28. 158 圖4-15 Polarization curves and corresponding power density plots of the batteries. 160 圖4-16 Hardened density of OPC and GP at different water to binder ratios.. 162 圖4-17 Weight loss of OPC and GP s at different water to binder ratios. 163 圖4-18 Porosity of OPC and GP at different water to binder ratios 165 表目錄 表1-1 波特蘭水泥各種類成份及性質[12] 5 表1-2 水泥成份組成表[13] 8 表1-3 波特蘭水泥加水後主要礦物所產生的水化反應[14] 10 表1-4 Properties of carbon nanotube and graphene[32; 33]. 22 表1-5 Comparison of different graphene preparation methods [21] 25 表1-6 Comparison of different graphene preparation methods (continued) [21] 26 表1-7 Methods for the oxidation of graphite to graphite oxide [39]. 29 表1-8 Comparison of the reducing effect of GO by different methods[43] 39 表1-9 無機聚合物之結構型式[70] 56 表2-1 纖維與奈米材料特性比較[71] 59 表2-2 Mix design for CNTs with other additives in cement-based composite. 65 表2-3 Fresh properties of nanocomposites. 66 表2-4 Mix design for CNTs in cement-based composite. 69 表2-5 Microstructure results of nanocomposites 77 表3-1 Chemical composition of the Type I cement 94 表3-2 渥太華砂粒徑分析 95 表3-3 HEMC Typical Physical Properties 95 表3-4 Specification of the polycarboxylate ether(PC) 96 表3-5 Proportions of GNPs and/or MWCNTs in cement composites 110 表4-1 Chemical analysis and physical properties of slag (%). 134 表4-2 Cement-based and geopolymer electrolyte formulations 142 表4-3 Effect of water to binder ratio on setting time. 147 表4-4 Effects of different water to binder ratios on compressive strength 148 表4-5 Effect of water to binder ratio on bulk resistance. 149 表4-6 Summary of the electrochemical performance results of the geopolymer, cement and soil electrolytes. 161

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