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研究生:巫明憲
研究生(外文):Wu, Ming-Sieng
論文名稱:聚丙二醇水性聚尿酯電解質之研究
論文名稱(外文):Study on Poly(propylene glycol) Based Waterborne Polyurethane as Solid Electrolytes
指導教授:溫添進
指導教授(外文):Ten-Chin Wen
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
畢業學年度:86
語文別:中文
論文頁數:121
中文關鍵詞:高分子電解質水性聚尿酯固態電解質複合式高分子電解質鋰鹽
外文關鍵詞:polymer electrolyteswaterborne polyurethanesolid electrolytecomposite polymer electrolytelithium salt
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本論文主要是在探討以聚丙二醇-二甲醇丙酸-3,3,5三甲基-2-環己
烯酮二異氰酸酯的水性聚尿酯作為固態高分子電解質的應用。 整個論
文可以分為三個部分,笫一個部分是在討論純水性聚尿酯的導電性質以及
其在吸收液態電解液時的行為;笫二部分則是進一步的針對純水性聚尿酯
的缺失,以滲混的方式做進一步的改良,並深入的探討改良後的高分子電
解質的形態以及其導電度的改良情形;第三個部分則是針對鋰鹽對高分子
電解質的影響以及鋰離子在高分子電解質中的角色作探討。 本研究所
用到的水性聚尿酯是利用本實驗室所開發出來的改良式丙酮法自行做聚合
。使用的材料包括平均分子量1000的聚丙二醇、二甲醇丙酸以及3,3,5三
甲基-2-環己烯酮二異氰酸酯,聚合成含有離子基的水性聚尿酯,加入的
液態電解液則是用1M LiClO4/PC。吸收實驗的應用則可以初步的瞭解水性
聚尿酯和液態電解液的關係;交流阻抗分析的使用,可以得知水性聚尿酯
的離子導電度。所得到的水性聚尿酯的離子導電度可以接近純液態的導電
度,但是其機械強度卻頗差。 複合式高分子電解質的使用,使得高分子
電解質的液態電解質含量不必很多,即可得到不錯的導電度,而依然保有
一定的機械強度。偏光顯微鏡的使用可以得知水性聚尿酯和聚氧化乙烯摻
混後的形態;利用簡單的吸收實驗可以知道在複合式高分子電解質中液態
電解液的分佈情形。 鋰離子在水性聚尿酯中的導電行為則是藉由了微
分掃描熱卡計、紅外線光譜儀、X射線光電子分光儀以及交流阻抗分析儀
等的材料分析,探討水性聚尿酯的形態、高分子內的氫鍵、鍵結能以及水
性聚尿酯的導電度,得知鋰鹽在高分子內的角色。
The investigation of poly(propylene glycol) (PPG)-based
waterbornepolyurethane (WPU(PPG)) consisting of PPG,
dimethylolpropionic acid (DMPA)and isophorone diisocyanate
(IPDI) as solid polymer electrolyte has beendone in this thesis.
The swelling behavior of WPU(PPG) impregnated with 1 M
lithiumperchlorate (LiClO4) in propylene carbonate (PC) solution
was first studied,because the extent of liquid electrolyte is
considered to be responsible forthe ionic conductivity of
polymer electrolytes. Afterwards, conductivitiesof the
corresponding WPU(PPG) electrolytes were obtained by using
alternatingcircuit (AC) impedance. A good conductivity of
10-2~10-3 S/cm can be achievedfor WPU(PPG) electrolyte
containing 84% LiClO4/PC, which possesses a poormechanical
strength. On the other hand, the composite electrolyte (CE),by
means of mixing WPU(PPG), PEO and LiClO4/PC, which contains
littleLiClO4/PC, possessing both a high conductivity of ca. 10-3
S/cm and a goodmechanical strength. Furthermore, in order to
clarify the interaction between WPU(PPG) andLiClO4 for its
further application, fourier-transform infrared spectroscopy(
FTIR), X-ray photoelectron spectroscopy (XPS), differential
scanningcalorimetry (DSC), and electrochemical impedance
spectroscopy (EIS) wereutilized to monitor the phase change of
this WPU with the doped LiClO4concentration. Significant changes
occur in the FTIR spectrum of the WPUwith the added salt
concentration above 1 mmol/g WPU, indicating that aninteraction
with the lithium cation within the hard segment and between
thehard and soft phases occurs. The soft segment Tg increases
with increasingLiClO4 through the examination of DSC. XPS
results reveal that the componentof nitrogen polaron sites (N+)
increases with increasing LiClO4, and that thesaturation level
of salt doping is evidenced by the mole ratio of componentC-O to
C=O; meanwhile, a rearrangement in long chain of the soft domain
hasalso been observed when this WPU is doped with LiClO4. EIS
results indicatean increase in bulk conductivity as the salt
concentration is increased. Thepresent study concluded that the
characteristic phase separation of the WPUis altered as a result
of the interaction of lithium cations within the polarhard
domains, and that the phase intermixing is promoted by the
coupling ofthe hard and soft phases.
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