研究生: |
林元凱 Yuan-Kai Lin |
---|---|
論文名稱: |
Li-Nafion黏著劑均勻包覆NCM正極材料之研究 Research on Conformal Coating of Li-Nafion Binder on NCM Positive Electrode Materials |
指導教授: |
黃炳照
Bing-Joe Hwang |
口試委員: |
吳溪煌
She-Huang Wu 蘇威年 Wei-Nien Su 潘俊仁 Chun-Jern Pan 林明憲 Ming-Hsien Lin 黃炳照 Bing-Joe Hwang |
學位類別: |
博士 Doctor |
系所名稱: |
工程學院 - 化學工程系 Department of Chemical Engineering |
論文出版年: | 2023 |
畢業學年度: | 111 |
語文別: | 中文 |
論文頁數: | 146 |
中文關鍵詞: | 高鎳正極材料 、Li-Nafion 、高倍率充放性能 、循環充放電穩定性 |
外文關鍵詞: | Ni-rich Positive Electrode Materials, Li-Nafion, Rate performance, Cycle Stability |
相關次數: | 點閱:352 下載:0 |
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全球主要經濟體積極推動降低對石化燃料的需求,促使新一波的能源轉型,而在發展轉型的路線上,提升鋰離子二次電池的能量密度成為重要的課題。高鎳正極材料具有超過210 mAh/g的高能量密度,因此而受到關注。但隨著鎳含量的提升,在充放電過程中,高鎳正極材料的劣化與容量的衰退也更為嚴重。黏著劑為鋰離子二次電池中不可或缺的元件,但目前商品化的PVDF僅提供物理性的黏合作用,未能對電極電化學性能有加成綜效。
在本研究中,選用具有陽離子傳導特性的Li-Nafion做為鋰離子二次電池高鎳正極材料 (NCM) 的粘著劑,並通過機械融合法將活性碳材均勻的包覆在 NCM表面 (NCM@C),從而優化了Li-Nafion在NCM@C表面上的包覆均勻性,進而降低電極內的介面阻抗。經由電化學測試,在6C速率下,NCM@C可獲得153.1 mAh/g放電容量,遠優於NCM使用傳統混漿電極的134.3 mAh/g。均勻的包覆不僅提升了倍率放電的性能,也延緩了電解液與正極材料表面的反應,而有較好的循環放電表現。在1C充放電速率下測試100次循環後,NCM@C的容量保持率為91%,優於傳統混漿NCM電極的88 %,進一步將充放電速率提升至6C經過100次循環後,NCM@C的容量保持率與傳統混漿的NCM電極比較由74 %提升至85 %,在高倍率放電下,均勻塗層改善的效果更加顯著。我們發現透過正極材料的表面塗層,來改善電極內的介面阻抗,可以提高倍率放電性能和循環壽命。這個研究中所使用的表面改質方法,無須經過多餘的清洗或是熱處理,提供一種快速、且穩定的操作技術,簡化了處理的程序與降低成本。儘管在一般低速充放電的電池使用狀況下效果較不顯著,但在高倍率下的充放電性能與循環壽命提升極為顯著,這為需要快速充放電能力的應用提供了一個具有潛力的方向。
最後本研究也顯示了在室溫下,使用Li-Nafion同時做為黏著劑與高分子電解質的測試,做為未來高分子電解質應用的方向。
Major global economies are actively pushing for a reduction in the demand for fossil fuels, leading to a new era of energy transformation. In the course of developing this transition, enhancing the energy density of lithium-ion batteries has become a crucial challenge. Nickel-rich positive electrode materials have attracted attention due to their high energy density exceeding 210mAh/g. However, as the nickel content increases, the degradation and capacity decay of nickel-rich positive electrode materials become more severe during the charging and discharging process. Additionally, binders are indispensable components in lithium-ion secondary batteries. However, the currently commercialized PVDF (polyvinylidene fluoride) only provides physical adhesion, lacking other desirable properties.
In this study, a novel process was developed for the conformal coating of a lithium-ion conductive lithiated Nafion (Li-Nafion) binder on a nickel-rich positive electrode material, namely LiNi0.83Co0.12Mn0.05O2 (NCM), for lithium-ion batteries (LIBs). Specifically, mechanofusion was first performed to first fabricate an active carbon coating (Super-P) over the surface of NCM, named as NCM@C, thereby optimizing the Li-Nafion coating on NCM@C and reducing the interface impedance between Li-Nafion and NCM. The electrochemical test results revealed that the 6C discharge capacity of NCM@C increased from 134.3 mAh/g to 153.1 mAh/g following the mechanofusion treatment, verifying that conformal and uniform Li-Nafion coating improved discharge rate performance as well as mitigated interactions between the electrolyte and positive electrode materials surface, leading to better cycle discharge performance. After 100 cycles at 1C charge/discharge tests, NCM@C boosted its capacity retention from 88% to 91%. Furthermore, after conducting 100 cycles of testing at a charge-discharge rate of 6C, the capacity retention of NCM@C increased from 74% to 85%. The improvement in the uniform coating had an even more pronounced effect under high-rate discharge conditions. This study confirmed that a positive electrode materials coating with conformal and high uniformity enables the alleviation of interface impedance between Li-Nafion and NCM, thereby increasing the discharge rate performance and cycle life of batteries. The surface modification method utilized in this study offers a fast and stable operational technique without excessive washing or heat treatment, thereby reducing processing steps and costs. Although the effects may not be significant under typical low-rate charge-discharge conditions, there is a notable improvement in charge-discharge performance and cycle life under high-rate conditions. This provides a promising direction for applications requiring rapid charge and discharge capabilities.
In the final part of this study, the testing of Li-Nafion as both a binder and a polymer electrolyte at room temperature, serving as a reference for future applications of polymer electrolytes.
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