博碩士論文 110324015 詳細資訊




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姓名 章晶寧(Ching-Ning Chang)  查詢紙本館藏   畢業系所 化學工程與材料工程學系
論文名稱 無機填料於聚偏氟乙烯-六氟丙烯共聚物/聚碳酸亞丙酯複合型固 態電解質於鋰電池之應用
(Applications of Inorganic Fillers in Poly (vinylidene fluoride)-hexafluoropropene/ Poly (propylene carbonate)-Based Composite Electrolyte Solid-State Lithium Batteries)
相關論文
★ 鈰摻雜之固態電解質Li7La3Zr2O12應用於鋰離子電池★ 運用芳香化合物與鋰金屬之化學預鋰化方法對鋰離子電池負極影響
★ 以雙深共熔溶劑系統對廢棄鋰離子電池進行選擇性回收及優化之研究★ Li7La3Zr2O12與聚偏氟乙烯-六氟丙烯共聚物/聚碳酸亞丙酯 複合型電解質應用於類固態鋰離子電池之研究
檔案 [Endnote RIS 格式]    [Bibtex 格式]    [相關文章]   [文章引用]   [完整記錄]   [館藏目錄]   至系統瀏覽論文 (2025-8-14以後開放)
摘要(中) 複合型的固態電解質結合高分子與無機填料(陶瓷材料、二氧化矽)之優點,特別是高分子主體PVDF-HFP與PPC具有良好的機械性質、穩定的電化學窗口等優勢,兩種材料可有效提升電池的電化學特性,並添加相較於商用電池極少量的離子液體,可降低固態電解質與電極的界面電阻,更接近全固態鋰電池的未來趨勢。
本研究之高分子由聚偏氟乙烯-六氟丙烯共聚物(Poly vinylidene fluoride-hexafluoropropylene,PVDF-HFP)作為主體,添加少量聚碳酸亞丙酯(Poly propylene carbonate,PPC)進行混摻,將兩者混合後塗佈並烘乾形成固態高分子電解質層作為對照組,實驗組則添加二氧化矽奈米材料(SiO2)作為被動填料,或是已添加已參雜金屬鉭(Ta)或金屬鋁(Al)之陶瓷材料(LLZTO、LLZAO)作為主動填料,探討無機填料加入高分子中形成複合型固態電解質,對於材料本身及電化學性質的影響。
實驗搭配NCM811為正極系統,鋰金屬為負極,於室溫下進行充放電分析。實驗結果發現SiO2作為被動填料可表現出較高分子優異的電化學特性。添加10wt% SiO2於PVDF-HFP/PPC中,可得低速比電容量(207.14 mAh/g @ 25 mA/g)、高速比電容量(122.79 mAh/g @ 300 mA/g)、離子導率(7.81 ×10-4 S/cm)、鋰離子遷移率(tLi+=0.43)。
另一種本身含有元素鋰之主動填料(LLZTO、LLZAO),其中又以添加10wt.%-LLZAO於PVDF-HFP/PPC有最佳電性表現:具備低速比電容量(228.87 mAh/g @ 25 mA/g)、高速比電容量(161.50 mAh/g @ 300 mA/g)、離子導率(8.84 ×10-4 S/cm)、鋰離子遷移率(tLi+=0.47)。
透過本研究得知,透過添加適量無機填料(SiO2、LLZTO、LLZAO)於固態高分子電解質,可使電性有明顯提升,皆有助於未來固態電解質之發展。
摘要(英) Lithium metal batteries (LMBs) have recently been regarded as a potential energy source. However, safety issues arising from the leakage of liquid organic solvents and the growth of lithium dendrites need to be addressed. Therefore, replacing liquid electrolytes with solid-state composite electrolytes (SCEs)1 may be a promising solution.
The SCEs in this study are mainly composed of poly-vinylidene fluoride-hexafluoropropylene (PVDF-HFP) and poly-propylene carbonate (PPC) and inorganic fillers such as silicon dioxide (SiO2) particles, Ta-Li7La3Zr2O12 (LLZTO) or Al-Li7La3Zr2O12 (LLZAO). The SCEs combine the advantages of good mechanical properties and a wide electrochemical window provided by polymers. Additionally, the inorganic fillers are used to reduce the crystallinity and enhance the Li+ transportation by forming a space-charge region and the acid-base interaction. At last, add a trace amount of ionic liquid relative to commercial lithium batteries in order to reduce the interface resistance between the membrane and electrodes.
A solid-state composite NCM811|SiO2-PVDF-HFP/PPC|Li battery exhibits an initial discharge capacity of 207.14 mAh/g @ 25 mA/g, 122.79 mAh/g @ 300 mA/g, ionic conductivity of 7.81×10-4 S/cm, and a lithium transference number of 0.43.
Another solid-state composite NCM811|LLZAO-PVDF-HFP/PPC|Li battery exhibits an initial discharge capacity of 228.87 mAh/g @ 25 mA/g, 161.50 mAh/g @ 300 mA/g, ionic conductivity of 8.84×10-4 S/cm, and a lithium transference number of 0.47.
關鍵字(中) ★ 鋰電池
★ 氧化物固態電解質
★ 複合型固態電解質
★ 單離子導體
關鍵字(英) ★ Lithium batteries
★ oxide-based solid-state electrolytes
★ solid-state composite electrolytes
★ single-ion conductor
論文目次 摘要 i
Abstract iii
目錄 v
圖目錄 ix
表目錄 xv
第1章 緒論 1
1-1 前言 1
1-2 研究動機 3
第2章 文獻回顧 7
2-1 正極材料-LiNi0.8Co0.1Mn0.1O2 (NCM811)介紹 7
2-2固態高分子電解質介紹 8
2-3複合型固態電解質介紹 16
2-3-1 不包含鋰離子之無機填料-被動填料 (SiO2) 16
2-3-2 包含鋰離子之無機填料-主動填料 (LLZO) 20
2-4無機陶瓷固態電解質介紹 24
2-5石榴石型(Garnet type)-Li7La3Zr2O12的發展 26
2-6石榴石型(Garnet type)-Li7La3Zr2O12的機制 28
2-7 Li7La3Zr2O12之優化-元素摻雜介紹 29
2-7-1 鉭(Ta)參雜LLZO 30
2-7-2鋁(Al)參雜LLZO 32
第3章 實驗方法 35
3-1實驗藥品 35
3-2實驗設備 36
3-3實驗步驟 37
3-3-1固態高分子電解質製備 37
3-3-2複合型固態電解質製備 37
3-3-3複合正極製備 38
3-3-4離子液體配置 (PMPFSI+ LiTFSI+ 1 wt.% LiDFOB) 39
3-3-5鈕扣電池組裝 39
3-4材料分析與鑑定 41
3-4-1粉末X光繞射儀 (Powder X-ray diffraction, PXRD) 41
3-4-2冷場發射掃描式電子顯微鏡(The field-emission scanning electron microscope, FE-SEM) 41
3-4-3感應耦合電漿放射光譜儀 (ICP-OES) 41
3-4-4熱穩定分析 (Thermogravimetric analysis, TGA) 41
3-4-5機械性質測試 42
3-5電化學性質分析與鑑定 43
3-5-1 循環充放電 43
3-5-2交流阻抗 (Electrochemical impedance spectroscopy, EIS) 43
3-5-3循環壽命測試 (The Cycling performance) 47
第4章 結果與討論 48
4-1 LiNi0.8Co0.1Mn0.1O2之分析與鑑定 49
4-2不同含量之被動填料(SiO2) 於電池性能之分析 51
4-2-1無機填料(SiO2)之分析 51
4-2-2複合型固態電解質之分析 52
4-2-3充放電分析 59
4-2-4交流阻抗之分析 65
4-2-5循環壽命之分析 69
4-3不同含量之主動填料(LLZTO或LLZAO) 於LiNi0.8Co0.1Mn0.1O2對於電池性能之分析 71
4-3-1無機陶瓷固態電解質(LLZTO、LLZAO)之分析 71
4-3-2複合型固態電解質之分析 76
4-3-3充放電分析 87
4-3-4交流阻抗分析 100
4-3-5循環壽命分析 107
第5章 結論與未來展望 110
第6章 附錄 112
6-1 主動填料(LLZAO)之粒徑分佈對於LiNi0.8Co0.1Mn0.1O2對於電池性能之分析 112
6-1-1充放電分析 113
6-2 PAMPS及鋰化後介紹 120
6-2-1實驗步驟 (高分子主體-PAMPS) 122
6-2-2 結果與討論 123
6-2-3固態高分子電解質(PAMPSLi-EO3AA)之分析 123
第7章 參考資料 135
參考文獻 第7章 參考資料
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指導教授 李岱洲 張仍奎(Tai-Chou Lee Jeng-Kuei Chang) 審核日期 2023-8-15
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