混合物實驗設計法配製高分子電解質與特性分析

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Title:	混合物實驗設計法配製高分子電解質與特性分析
Other Titles:	The Polymer Electrolytes are Prepared by the Mixture Design Method and Analyse the Properties
Authors:	蕭偉利 Hsiao, Wei-Li
Contributors:	杜景順 Do, Jing-Shan 東海大學化學工程與材料工程學系
Keywords:	高分子電解質;電解質;混合物實驗設計法 SPE;polymer electrolyte;mixture design
Date:	1997
Issue Date:	2011-06-15T02:37:25Z (UTC)
Abstract:	摘要本論文首先利用混合物實驗設計法探討PEO-LiCF3SO3-Tetraglyme 和PEO-LiCF3SO3-Tetraglycol兩系統之最佳導電度組合。利用Zeolite 和g-Al2O3添加至高分子電解質系統中，討論其對高分子電解質性質之影響，最後將製備之高分子電解質組裝成Li / SPE / MnO2電池，探討其放電特性。在混合物實驗設計法中改變PEO-LiCF3SO3-Tetraglyme和 PEO-LiCF3SO3-Tetraglycol高分子電解質之成分比例，實驗結果顯示，當電解質組成範圍為15-67% (wt) PEO、10-20% LiCF3SO3及34-83% Tetraglyme與10-77% PEO、10-20% LiCF3SO3及21-88% Tetraglycol 可得最佳導電度。22.0PEO / 19.0LiCF3SO3 / 59.0Tetraglyme與20.0 PEO / 17.0LiCF3SO3 / 63.0Tetraglycol（wt%）高分子電解質膜有較佳的室溫導電度，分別為8.23×10-5S / cm及7.37×10-5S / cm。另外，添加Zeolite和g-Al2O3於高分子電解質中，可增加電解質之機械性質，且可增加導電度。由線性掃描伏安法分析製備之高分子電解質之氧化分解電位，其分解電位介於4.8V~5.4V之間。此外，添加Zeolite有增加氧化分解電位的能力。分析製備之高分子電解質鋰離子傳遞係數發現，在PEO-LiCF3SO3- Tetraglyme系統中，當22.0PEO / 19.0LiCF3SO3 / 59.0Tetraglyme + Zeolite（Zeolite / (PEO+LiCF3SO3 + Tetraglyme)=0.2）之下，在 55℃具有最大之tLi+，其值為0.27；而PEO-LiCF3SO3-Tetraglycol系統中，當20.0PEO / 17.0LiCF3SO3 / 63.0Tetraglycol + Zeolite （Zeolite / (PEO+LiCF3SO3 + Tetraglycol)=0.2）時，55℃下之最大 tLi+則為0.26。傳遞係數tLi+值會隨導電度的增加而增加，亦會隨著溫度升高而逐漸增加。利用循環伏安法分析鋰離子的沈積反應，由實驗結果發現鋰離子的沈積反應為完全不可逆之行為。由此分析中可求得鋰離子在22.0PEO / 19.0LiCF3SO3 / 59.0Tetraglyme + g-Al2O3（g-Al2O3 / (PEO+LiCF3SO3 + Tetraglyme)=0.1）與20.0PEO / 17.0LiCF3SO3 / 63.0Tetraglycol + g-Al2O3（g-Al2O3 / (PEO+LiCF3SO3 + Tetraglycol)=0.2）高分子電解質中的擴散係數分別為1.89×10-8cm2 / s與1.66×10-8cm2 / s。並求得兩系統中之ana與k0之關係式，分別為ana=3.17×10-2及 k0 =2.10×10-5 exp (-1.07 E0)與ana=3.05×10-2及 k0 =1.77×10-5 exp (-1.03 E0)。將製備所得之高分子電解質組裝成Li / SPE / MnO2一次電池，發現仍須在高於55℃之環境下才會有較高的放電電容量，且其放電速率應該小於0.382 mA / cm2。在自放電現象方面，添加Zeolite和g-A2O3於高分子電解質中，發現能抑制自放電現象，當添加Zeolite和g-A2O3至PEO- LiCF3SO3-Tetraglycol系統中，可使自放電率由6.2％減少為5.1％與5.3 ％。在55℃時以20.0PEO / 17.0LiCF3SO3 / 63.0Tetraglycol + Zeolite （Zeolite / (PEO + LiCF3SO3 + Tetraglycol)=0.2）組裝成電池，具有最佳的放電電容量，其值為2.10 mAh。 Abstract The maximum coductivity compositions of PEO-LiCF3SO3-Tetraglyme and PEO-LiCF3SO3-Tetraglycol were studied in this thesis by using the mixture design method. Zeolite and g-Al2O3 were added to modify the solid polymer electrolytes（ SPE）. Using prepared SPE, the discharge characteristics of Li / SPE / MnO2 was also studied. The maximum conductivity composition intervals of two SPE systems were experimentally found as 15-67% (wt) PEO 、10-20% LiCF3SO3 and 34-83% Tetraglyme for PEO-LiCF3 SO3-Tetraglyme as were as 10-77% PEO 、10-20% LiCF3SO3 and 21-88% Tetraglycol for PEO-LiCF3SO3-Tetraglycol. The experimental also indicated that the maximum conductivities of PEO-LiCF3SO3-Tetraglyme and PEO-LiCF3SO3-Tetraglycol were 8.23×10-5S / cm and 7.37×10-5S / cm, respectively, and its compostions were 22.0PEO / 19.0LiCF3SO3 / 59.0Tetraglyme and 20.0 PEO / 17.0LiCF3SO3 / 63.0Tetraglycol（wt%）at room temperature. In addition, the mechainical characteristics and conductivity increased when Zeolite and g-Al2O3 were added to SPE. The decomposition voltages of the polymer electrolytes were obtained by the linear sweep voltammetry in the rang of 4.8V ~ 5.4V. The decomposition voltages of SPE increased as Zeolite added. The experimental results revealed that the maximum Li+ transfer numbers（tLi+） for the systems of PEO-LiCF3SO3-Tetraglyme, 22.0PEO / 19.0LiCF3SO3 / 59.0Tetraglyme + Zeolite（Zeolite / (PEO+LiCF3SO3 + Tetraglyme)=0.2）and PEO-LiCF3SO3-Tetraglycol, 20.0PEO / 17.0LiCF3SO3 / 63.0Tetraglycol + Zeolite（Zeolite / (PEO+LiCF3SO3 + Tetraglycol)=0.2）were 0.27 and 0.26, respectively, at 55℃. The Lithium ion transport number increased with increasing conductivity and temperature. The total irreverisible reaction was found in the deposition of Li+ at stainless steel by the results of cyclic voltammetry. Using cyclic voltammetry, the diffusion coefficient of Li+ in the 22.0PEO / 19.0LiCF3SO3 / 59.0Tetraglyme + g-Al2O3（g-Al2O3 / (PEO+LiCF3 SO3 + Tetraglyme)=0.1） and 20.0PEO / 17.0LiCF3SO3 / 63.0Tetraglycol + g-Al2O3（g-Al2O3 / (PEO+LiCF3SO3 + Tetraglycol)=0.2） were obtained as 1.89×10-8cm2 / s and 1.66×10-8cm2 / s, respectively. The parameter of ana were also evaluated as 3.17×10-2 and 3.05×10-2, and the relationships of k0 were obtained as 2.10×10-5 exp (-1.07 E0) and 1.77×10-5 exp (-1.03 E0). The better discharge capacity of Li / SPE / MnO2 was found when the operating temperature was larger than 55℃, and the discharge current density less than 0.382 mA / cm2. The results indicated that Zeolite and g-Al2O3 can inhibit the self-discharge of Li / SPE / MnO2. Comparison with PEO - LiCF3SO3 - Tetraglycol with no additive, the self-discharge fraction decreased from 6.2％ to 5.1％ and 5.3％, respectively, when Zeolite and g-Al2O3 were added to modify this SPE. When 20.0PEO / 17.0LiCF3SO3 / 63.0Tetraglycol + Zeolite （Zeolite / (PEO + LiCF3SO3 + Tetraglycol)=0.2） was used to prepare Li / SPE / MnO2, the maximum discharge capacity was found as 2.10 mAh at 55℃.
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