雙馬來醯亞胺(N,N’-bismaleimide-4,4-diphenylmethane , BMI )為基底形成的超分歧結構，因
其可以提供良好的機械性質、熱穩定性而作為添加劑被應用在鋰離子電池中。先前的研究
中，研究團隊藉由雙馬來醯亞胺可以其兩個未端碳-碳雙鍵與巴比妥酸( Barbituric acid , BTA )上的活性氫進行麥可加成反應或自由基加成聚合反應後形成的高分子寡聚物
(STOBA)，做為鋰離子電池正極的電極添加劑使用，並觀察到在首圈充電過程中該寡聚物
會進行聚合反應並對充電曲線造成影響。此種影響可以提高鋰離子電池的循環壽命並進一
步的在高溫環境中進行交連作用產生新的電極-電解液介面，提升電池的性能與安全性。因
此，針對該高分子寡聚物在過程中進行的聚合反應對於掌握該高分子寡聚物以及改善鋰離
子電池的安全性問題扮演著關鍵的腳色。本研究大致分為四個部分來探討此一現象：
首先，本研究將 BMI/BTA 分別於 353 K 與 403 K 下進行合成，所得之高分子寡聚物分
別為 polymer A 與 polymer B，並探討其在鋰離子電極中的電化學與熱化學性質。在此系
統下，polymer A 的結構直接麥可加成反應影響，polymer B 的結構則受麥可加成反應與第
二麥可加成反應影響。表面電漿共振的模擬結果顯示 polymer B 具有較高的結合速率常數。
polymer A 系統中有許多未進行反應的官能基團，會於首圈充放電過程中陰極材料表面形
成第二個保護層，使得電池的熱穩定性以及循環壽命表現優於 polymer B。
第二 ，本 研究使 用含有 一個 CH2 基團 的 1,3 巴比 妥酸( 1,3-Dimethylbarbituric acid , 1,3-DMBTA ) 和 含 有 兩 個 NH 基 團 的 5,5 巴 比 妥 酸 ( 5,5-Dimethylbarbituric acid , 5,5-DMBTA )與BMI分別聚合形成polymer C與polymer D，並添加於LiNi0.6Mn0.2Co0.2O2
(NMC)陰極材料中探討其熱化學穩定性。研究結果顯示 polymer D 會與活性材料中的過渡
金屬離子形成錯合物，可有效協助電子傳導並改善電極材料發生的熱降解問題。
第三，此部分探討藉由甲基取代巴比妥酸( Barbituric acid , BTA )上 N1、N3 的活性氫位置，
對於鋰離子電池陰極材料安全性質的影響。結果顯示與 polymer A 相比，甲基取代後的結
構會在第一圈充放電過程中於陰極料表面進行自身聚合。polymer C 的結果顯示該分子由於
沒有自由的氫原子可以於 NMC 陰極材料表現進行自身聚合，導致其在電池循環壽命與安
全性的表現上較差。
第四、本研究探討 dimethyl 對 BTA 的 C5 位置進行改質後的影響。和 polymer D 不同，以
polymer B 進行表面修飾的樣品，由於其高分歧結構對於鋰離子的擴散較差，因此不會與陰
極材料表現形成錯合物或受陰極材料的影響進行自身聚合，使其在電池性能的表現上較差。
本研究結合光學、電化學、熱化學以及同步輻射分析等數種不同的特性分析技術來探討鋰
離子電池電極添加劑 STOBA 的最佳運作結構與條件。

N,N’-bismaleimide-4,4’-diphenylmethane (BMI) based polymers exhibiting a
hyperbranched structure that offers excellent mechanical properties, chemical resistance, thermal
stability and attractive performance in lithium-ion batteries (LIBs). With the reactive two
terminals, BMI can be polymerized with active H-atom containing species such as barbituric acid
(BTA) and it's derivative via the Michael addition, Aza-Michael addition and free radical
reaction mechanisms. Once the cathode materials are coated with such polymers (known as
STOBA), an electrochemical reaction causes further polymerization in first charging step; then
enhances the performance in successive cycles and thermally cross-linked at high temperature to
prevent the electrode-electrolyte interaction. Thus, monitoring its polymerization reactions and
studying the detail safety mechanism could play a vital role in optimizing the working condition
of STOBA in the development of LIB technology. This thesis contains four motivations. The first motivation is the kinetic study of BMI/BTA synthesized at 353 K (polymer A)
and at 403 K (polymer B), its thermal and electrochemical impact on LIBs. The Michael addition
reaction controls the overall process with insignificant Aza-Michael addition product in polymer
A; however, both reaction mechanisms are operative in polymer B fashioning an extra
cross-linked adduct. The simulation result from surface plasma resonance indicates the high
binding rate constant is obtained in polymer B. Owing to the presence of unreacted functional
group, the cathode material treated with polymer A could undergo electrochemical reactions in
the first cycle and form secondary protective layer by virtue of thermal heating; it has shown
phenomenal thermal stability and good performance as compared to the cathode modified with
polymer B.
The second motivation is probing the surface properties and thermochemical effect of
LiNi0.6Mn0.2Co0.2O2 (NMC) cathode material modified with the polymer obtained from BMI with
1,3-dimethylbarbituric acid (1,3BTA) and 5,5-dimethylbarbituric acid (5,5BTA). It is noteworthy
that 1,3BTA contains only one -CH2 group, whereas 5,5BTA contains two -NH groups per
molecule. Accordingly, BMI/5,5BTA (polymer D) showed the structural difference and forms
the stable complex with transition metal ions of active material; fostered the ionic as well as
electronic transfer and prohibited the thermal degradation of the battery as compared to cathode
treated with BMI/1,3BTA (polymer C). The third motivation is the detail investigation on the effect of methyl substitution at N1, N3 position of BTA on the safety mechanism of cathode material. Comparing with the cathode
modified by polymer A (un-substituted BTA; with two free N-H groups) could electrochemically
self-polymerize in first charge/discharge process and form rigid structure upon thermally heated
at high temperature. However, the structure of polymer C (di-substituted) is noticeable affects
the surface kinetics of NMC and has no free H-atoms to initiate self-polymerizations. These lead
to poor safety and cycle performance while the overall result of battery modified with polymer A
shows improved cycle performance and minimized safety issues. The fourth and last motivation is the analysis of the effect of dimethyl substitution at C5
comparing with un-substituted BTA on the safety mechanism of LIBs. According to the result, the cathode surface modified by polymer B (un-substituted) could not electrochemically and
thermally polymerize in charge/discharge and at elevated temperature. Because of the
hyper-branched complex initially formed, it tends to depreciate Li+
-ion diffusion and bears lower
reversible capacity; nevertheless, its cycle capacity and rate capability becoming superior in the
successive cycle. In the case of polymer D (di-substituted), the structure is originally having a
good surface attachment so that it could improve the ionic and electronic conductivity. Therefore, this cathode material increases the safety of battery without affecting discharge capacity. In this work, there are various modern characterization techniques such as
electrochemical, optical, thermal, spectroscopy and synchrotron radiation have been used
concurrently in order to optimize and design the best working conditions of STOBA as cathode
additives in LIBs.

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