使用硫化物電解質 (SE) 的全固態電池 (ASSB) 比使用有機電解質的傳統鋰離子電池更穩定、更安全。它們的應用潛力受到高度重視。常用的製膜方法可以大致分為濕式塗佈工藝以及乾式塗佈工藝。為了擴大硫化物電解質的生產，提高其能量密度，建立濕法塗佈法更符合工廠產線的設計，以取代過去用於製造電解質膜的粉末壓製法。低極性溶劑和聚合物可以形成更高離子電導率的硫化物固體電解質膜。目前從研究階段擴展成大面積製膜的最大問題與挑戰，是如何從各式高分子中選出合適的黏合劑，在導離度、機械強度以及適用的最低電解質膜厚度之間取得最佳的平衡值，以及建立一個明確的評估電解質膜的研究系統。
本研究首先將電解質膜進行混漿製程優化，選擇出適當的混漿方法、材料粒徑大小以及塗佈基材。由二甲苯(Xylene, XYL)作為溶劑，苯乙烯乙烯丁烯苯乙烯(SEBS)作為黏合劑以及硫化物固體電解質為Li6PS5Cl (LPSC)。透過這些製程參數的調整，成功製備出尺寸為22 cm× 6 cm、厚度小於100 μm的硫化物固體電解質複合片材。此外也開發了一個新型的脫膜方法，成功製出尺寸為6 cm × 8 cm獨立式電解質膜(free-standing film)，方便電解質膜性能之研究。需要注意的是，黏合劑會影響硫化物固體電解質薄膜的力學性能，阻礙其鋰離子傳導，降低循環電化學性能。揮發性溶劑二甲苯也需要快速製造以保持複合漿料的可加工性。因此，在黏合劑的選定上我們也列出了初步快速篩選的條件，分別為分子量、機械性質以及黏合劑與材料相容性問題，最重要的是混合過程中不產生化學反應。由上述條件最後篩選出聚異物二烯(Polyisoprene, PI)作為新型LPSC電解質膜之黏合劑。
透過新型LPSC電解質膜建立完整電解質膜測試及研究系統，電解質膜在PI比例為5 %時，經由熱處理後有較高的導離度6.37×10-4 S/cm，在溫度80 ˚C下擁有最高的導離度2.46×10-3 S/cm，與商用LPSC錠狀電解質導離度相近。最後透過EIS和拉身試驗評去選擇電池組裝之比例，以雙層塗佈技術製備極片，以KP cell進行全固態電池組裝，第一層正極材料使用的是LNO@NCM811高鎳三元材料，其為表面塗有LiNbO3保護層的鎳鈷猛三元材料(LiNi8Co1Mn1O2，NMC(811))，第二層固態電解質使用添加3% PI之新型LPSC電解質膜，負極使用銦金屬。充電區間2 V~3.9 V、0.05 C，於室溫下施予100 MPa之外壓，首圈電容達122.72 mAh/g，經10圈充放電後可維持63.3 %以上的維持率。雖然在電池的壽命上還有很大的優化空間，但透過電解質膜製程與黏合劑優化分析以及新建立的獨立式電解質膜製程，本研究成功製備出實驗室首片可彎曲性自力式電解質薄膜。

關鍵字：鋰離子電池，硫化物固態電解質，硫銀鍺礦，硫化物電解質膜，全固態電池

All-solid-state batteries (ASSBs) using sulfide electrolytes (SE) are more stable and safer than conventional Li-ion batteries using organic electrolytes. Their application potential is highly valued. Commonly used film forming methods can be roughly divided into wet coating processes and dry coating processes. In order to expand the production of sulfide electrolytes and increase their energy density, the wet coating method was established to be more in line with the design of the factory production line to replace the powder pressing method used to manufacture electrolyte films in the past. Low-polarity solvents and polymers can form sulfide solid electrolyte composite films with higher ionic conductivity. At present, the biggest problem and challenge in expanding from the research stage to large-area film production is how to select suitable adhesives from various polymers. To achieve the best balance between conductivity, mechanical strength, and applicable minimum electrolyte film thickness, and to establish a clear research system for evaluating electrolyte films.
In this study, the slurry mixing process of the electrolyte film was optimized first, and the appropriate slurry mixing method, material particle size and coating substrate were selected. Xylene (XYL) is used as the solvent, styrene ethylene butene styrene (SEBS) is used as the binder, and the sulfide solid electrolyte is Li6PS5Cl (LPSC). Through the adjustment of these process parameters, a sulfide solid electrolyte composite sheet with a size of 22 cm × 6 cm and a thickness of less than 100 μm was successfully prepared. In addition, a novel stripping method was also developed, and a free-standing film with a size of 6 cm × 8 cm was successfully fabricated, which facilitates the study of the properties of the electrolyte film. It should be noted that the binder will affect the mechanical properties of the sulfide solid electrolyte film, hinder its ion conductivity, and reduce the cycle electrochemical performance. The volatile solvent xylene also needs to be manufactured quickly to maintain the processability of the composite slurry. Therefore, in the selection of binders, we also listed the conditions for preliminary rapid screening, which are molecular weight, mechanical properties, and compatibility between binders and materials. The most important thing is that no chemical reaction occurs during the mixing process. From the above conditions Polyisoprene (PI) was screened out as a new type of binder for LPSC composite films.
A complete electrolyte film testing and research system is established through the new LPSC electrolyte film. When the PI ratio of the film is 5 %, the conductivity after heat treatment is 6.37×10-4 S/cm. And at a temperature of 80 ˚C, it has the highest conductivity of 2.46×10-3 S/cm, which is similar to the conductivity of commercial LPSC ingot electrolyte. Finally, the ratio of battery assembly is selected through EIS and tensile test evaluation, electrode sheets are prepared by double-layer coating technology, and KP cell is used for all-solid-state battery assembly. The first layer of cathode material uses LNO@NCM811 high-nickel ternary material. It is a nickel-cobalt-manganese ternary material (LiNi8Co1Mn1O2, NMC(811)) coated with a LiNbO3 protective layer. The second layer of solid electrolyte uses a new LPSC¬ composite film with 3% PI added, and the anode uses indium metal. The charging range is 2 V~3.9 V, 0.05C, and an external pressure of 100 MPa is applied at room temperature. The capacity of the first cycle is as high as 122.72 mAh/g. After 10 cycles of charging and discharging, the retention rate is more than 63.3%. Although there is still a lot of room for optimization in battery life, the optimization analysis of the electrolyte film process and the binder and the newly established free standing film process, this study successfully prepared the first flexible self-supporting electrolyte membrane in the laboratory.
Key words： Lithium-ion battery, sulfide solid-state electrolyte, argyrodite, sulfide-electrolyte composite membrane, all-solid-state battery.

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