- 學位論文
具螺雙茚滿衍生物之高分子薄膜於滲透蒸發與鋰電池之應用
Polymer Membranes Based on Spirobisindane Derivatives for Pervaporation and Lithium Battery
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摘要
本論文開發具螺雙茚滿結構衍生物之目的為在薄膜材料中產生更多自由體積與微觀孔隙並促進分子鏈移動，用以提升當前高分子薄膜材料用於環保及綠能方面效能。合成方面利用強酸methylsulfonic acid (MSA)將bisphenol A (BPA) 快速轉化為具有剛性螺旋扭曲結構之3, 3, 3', 3'-tetramethyl-1, 1'-spirobisindane-6, 6'-diol (TSD)，再導入不同官能基合成多樣化單體與高分子衍生物並製備高分子薄膜。高分子薄膜應用之分析及探討分成二個部份，第一部份用於水/醇混和溶液滲透蒸發分離效能探討，有利於水資源回收再利用。第二部則用於鋰電池之全固態高分子電解質，並於配方及製程調整進行深入探討。 第一部分將氧化石墨烯以具螺雙茚滿結構之二胺4,4'-((3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-6,6'-diyl)bis(oxy))dianiline (TTSD)與二酚(TSD)單體進行改質，並與未具有旋轉扭曲結構之BPA改質氧化石墨烯進行比對，結合旋轉塗佈法於基材膜上製備應用於醇類脫水之聚醯亞胺滲透蒸發奈米複合薄膜，分析材料內部自由體積尺寸、分佈，以探討多層結構與化學組成之變化，進而了解自由體積與分離效能之間的關聯性並由正電子湮滅壽命譜加以驗證。較大螺雙茚滿結構所造成的立體障礙可阻礙分子鏈間的堆疊與排列，進而於材料內部中產生較多空間以提升自由體積。改質氧化石墨烯TTSD-GO的導入使聚醯亞胺奈米複合薄膜於25 °C進行70 wt %異丙醇水溶液滲透蒸發操作之滲透蒸發通量由619.3 ± 124.0 g∙m-2h-1上升至915.5 ± 44.8 g∙m-2h-1，而滲透端水濃度仍然保持約99 wt%。 第二部分同樣由TSD起始，發展出帶有可進行熱開環交聯反應之新型氧代氮代苯并環己烷單體6,6'-(6,6,6',6'-tetramethyl-6,6',7,7'-tetrahydro-2H,2'H-8,8'-spirobi[indeno[5,6-e][1,3]oxazin]-3,3'(4H,4'H)-diyl)bis(hexan-1-ol) (TSBZ6D)、2,2'-((6,6,6',6'-tetramethyl-6,6',7,7'-tetrahydro-2H,2'H-8,8'-spirobi[indeno[5,6-e][1,3]oxazin]-3,3'(4H,4'H)-diyl)bis(4,1-phenylene))diacetonitrile (TSBZBC)與4,4'-(6,6,6',6'-tetramethyl-6,6',7,7'-tetrahydro-2H,2'H-8,8'-spirobi[indeno[5,6-e][1,3]oxazin]-3,3'(4H,4'H)-diyl)dibenzonitrile (TSBZBN)，並成功在開環後作為半網狀互穿式高分子應用於鋰電池之全固態高分子電解質solid polymer electrolytes (SPEs)。當與polyethylene oxide (PEO)電解質結合時由TSBZ6D所創造的半網狀互穿式s-IPN結構使PEO-TSBZ6D (PT)複合高分子固態電解質之機械性質相較於PEO/lithium salt之樣品大幅提升(> 300% in tensile stress及 1100% in tensile strain)。對稱電池Li|PT|Li之電化學測試結果顯示PT SPEs 有效緩解鋰枝晶所造成的短路問題，而全固態鋰離子電池LiFePO4|PT|Li效能可於80 °C達比容量166 mAh g−1 (0.1 C) 及有潛力的循環穩定性。具有苯乙腈官能基之Li|BC20|Li 320可於0.1 mA cm-2下連續循環2700小時，並LiFePO4| BC20|Li效能可於80 °C充放50圈後仍有87%的比容量保留率。 此外，為了進一步優化電解質穩定性，在本論文第三部分中以高極性電紡β相poly(vinylidene fluoride-co-hexafluoropropylene) (β-PVDF-HFP)奈米纖維顯著提升高分子固態電解質的機械性質與鋰負極的穩定性，高極性電紡絲有助於鋰離子遷移並能夠減少鋰金屬嵌入/脫出界面枝晶的形成，同時提高正極間的電化學界面穩定性，除此亦可結合第二部分所開發之材料提升電池效能。本研究為新穎性的材料設計提供可行性平台，由相同核心出發，以有機合成法可針對所求導入所需官能基設計新型單體抑或是高分子材料，使此核心概念具備巨大發展空間。
並列摘要
The 3, 3, 3', 3'-tetramethyl-1, 1'-spirobisindane-6, 6'-diol (TSD) monomer with a spiro-twisted structure in this study was quickly converted from bisphenol A (BPA) by using methanesulfonic acid. The derivatives prepared with the rigid and bulky nature of the spiro-twisted structure in TSD can directly increase the fractional free volume in the materials. The TSD molecular can be converted into spiro-twisted benzoxazine derivatives bearing with different functional group. Accordingly, the subsequent molecular modification can be used to prepare derivatives or polymers with specific properties. The main purpose about the development of the functionalized spirobisindane derivatives is to create more fractional free volume and micropores to promote the movement of the polymer chain. It can be used to enhance the performance of the current polymer membrane in environmental protection and green energy. In terms of synthesis, the organic synthesis way is used to synthesize a series of monomers along with the purification and identification. Furthermore, the functional polymers are fabricated by polymerization thereby using the solvent casting process to obtain the polymer membrane. The analysis and discussion of the application of polymer membrane is divided into two parts. The first part uses the functionalized composite polymer membrane to study the separation of water/alcohol mixtures, which is conducive to the concept of water recycling and reuse. The second part is for the application of polymer electrolytes in lithium ion batteries, and in-depth discussion on the formulation and process adjustments. First of all, the graphene oxides were modified by spirobisndine-containing diamine 4,4'-((3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-6,6'-diyl)bis(oxy))dianiline (TTSD) and diol TSD, then compared with the graphene oxide which modified by the BPA without spirobiindane structure. Afterwards, combining the spin-coating process to fabricate the polyimide composite membrane onto the polysulfone substrate for alcohol/water mixtures pervaporation. The size and distribution of the fractional free volume inside the material were analyzed and the changes in the multilayer structure and chemical composition were also be explored. Accordingly, the correlation between the fractional free volume and the separation efficiency were discussed and verified by the positron annihilation lifetime spectroscopy. The larger steric obstacles of the spiro-twisted structure can hinder the stacking and arrangement of polymer chains, thereby creating more space in the material to increase the fractional free volume. The incorporation of the modified TTSD-GO made the composite polyimide membrane obtain the increase of the pervaporation flux from 619.3 ± 124.0 g∙m-2h-1 to 915.5 ± 44.8 g∙m-2h-1 with the water concentration in permeate keeping about 99 wt% (Feed=70 wt% aqueous isopropanol solution at 25°C). The crosslinkable benzoxazine monomer 6,6'-(6,6,6',6'-tetramethyl-6,6',7,7'-tetrahydro-2H,2'H-8,8'-spirobi[indeno[5,6-e][1,3]oxazin]-3,3'(4H,4'H)-diyl)bis(hexan-1-ol) (TSBZ6D), 2,2'-((6,6,6',6'-tetramethyl-6,6',7,7'-tetrahydro-2H,2'H-8,8'-spirobi[indeno[5,6-e][1,3]oxazin]-3,3'(4H,4'H)-diyl)bis(4,1-phenylene))diacetonitrile (TSBZBC) and 4,4'-(6,6,6',6'-tetramethyl-6,6',7,7'-tetrahydro-2H,2'H-8,8'-spirobi[indeno[5,6-e][1,3]oxazin]-3,3'(4H,4'H)-diyl)dibenzonitrile (TSBZBN) has been successfully synthesized from TSD. The TSBZ6D was successfully fabricated the solid polymer electrolytes (SPEs) which possessed the semi-interpenetrating polymer network (s-IPN) with the PEO. Compare with the pristine PEO/lithium salt SPE, the s-IPN structure made the PEO-TSBZ6D (PT) SPE obtained large enhance in mechanical properties (> 300% in tensile stress and 1100% in tensile strain). The electrochemical properties of symmetric sample Li|PT|Li indicated that the PT SPEs can effectively alleviate the short circuit problem caused by the lithium dendrite growth thereby the all solid state lithium ion battery LiFePO4|PT|Li possessed 166 mAh g−1 (0.1 C, 80 oC) and the promising cycle stability. The Li|BC20|Li sample by using PEO-TSBZBC (BC) SPE with benzyl cyanide functional group can be continuously cycled at 0.1 mA cm-2 for 2700 hours. The performance of LiFePO4|BC20|Li can retain 87% of its original specific capacity value after 50 cycles in charge and discharge test at 80 °C. The high polar poly(vinylidene fluoride-co-hexafluoropropylene) (β-PVDF-HFP) nanofiber layer significantly improves the mechanical properties of the SPE and the stability of the lithium negative electrode. The high polarity electrospinning nanofiber facilitates the migration of lithium ions and can reduce the formation of dendrites, while improving the positive electrode stability of the electrochemical interface between the cathode material. This concept also used in this study to improve the material performance. This research provides a feasibility platform for novel material design. Starting from the same monomer TSD, the organic synthesis can be used to introduce the required functional groups according to the requirements, so that this core concept has a huge development space.
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