鋁電池具有理論容量高，安全性好、成本低等優點，是新一代儲能技術的代表。設計和開發高比能、綠色可持續正極電極材料是構建高性能鋁離子電池的關鍵。氮氧自由基（TEMPO）聚合物作為典型有機正極材料已被廣泛應用于鋰離子電池、鈉離子電池、鋅離子電池等電池體系，并表現出高電壓、高功率、綠色可再生特性。然而，由于多數氮氧自由基在路易斯酸有機電解液中電化學氧化還原不可逆，使其無法應用于鋁離子電池正極材料。例如，在酸性Al(OTf)3乙腈電解液中，TEMPO歧化成TEMPO+與 TEMPO-，而后者與Al(OTf)3配位形成穩定的[Al(OTf)3TEMPO]-絡合物，其較高的氧化電位導致TEMPO電化學氧化還原不可逆而無法應用于鋁電正極。
解決TEMPO電極材料在Al(OTf)3路易斯酸體系中的電化學氧化還原可逆性的關鍵問題后，他們制備經典TEMPO官能化聚合物PTMA（圖2a）正極材料并嘗試構建水系鋁離子電池。電池測試表明：雖然疏水性聚酯結構PTMA在水系電解液中無法溶脹，表現出極高的電子轉移阻抗（~100 kΩ），嚴重阻礙了離子傳輸與電池充放電（圖2b），但在Al(OTf)3誘導歧化反應后生成TEMPO+與 [Al(OTf)3TEMPO]- 離子，賦予PTMA一定的親水性，顯著降低電子轉移阻抗（~10 kΩ），實現了PTMA正極的正常充放電（圖2b & c）。SEM表征佐證了相關電化學結果：未經充放電時PTMA聚合物在導電碳納米管表面呈現疏水團聚狀，經歧化活化與充放電后PTMA在水系電解液中溶脹并均勻包覆于導電碳納米管表面（圖2 d-g），有效促進電解質傳輸。綜上，PTMA歧化活化過程對提高電解質鹽在疏水PTMA電極中的離子傳輸，實現PTMA鋁離子電池充放電至關重要。
該電池提供大于1.25 V的輸出平臺電壓和接近理論的110 mAh g-1比容量（圖3a & b）。此外，PTMA鋁離子電池展現出優異的倍率性能，在8 C的高倍率條件下仍保有理論容量的81%，且在超過800次的充放電循環中每圈容量損失僅為0.028% （圖3c）。此外，PTMA鋁離子電池也表現出優異的阻燃性能和空氣穩定性。該研究為開發鋁基高能量、功率密度動力電池及高安全性大型儲能電站提供新方案。
上述成果發表于Journal of the American Chemical Society期刊；碩士研究生蔣尚旭和謝逸輝為共同第一作者，張凱博士和澳大利亞弗林德斯大學賈中凡教授、Michelle L. Coote教授為共同通訊作者，浙江理工大學為第一完成單位。
論文鏈接：https://doi.org/10.1021/jacs.3c04203
作者簡介
張凱
2018年于澳大利亞昆士蘭大學獲理學博士學位；2018-2020年在美國約翰霍普金斯大學開展博士后研究。2020年加入浙江理工大學化學與化工學院，任特聘副教授。主要研究領域為能源和高分子化學，研究興趣包括鋁離子電池、聚合物基柔性電池、有機水系液流電池等的機理研究和結構設計。以通訊作者/第一作者身份在J. Am. Chem. Soc., ACS Energy Lett., Energy Storage Mater., J. Mater. Chem. A, Chem. Eng. J.等學術刊物上發表論文十余篇，受到了國內外學術界的廣泛關注。
Zhongfan Jia（賈中凡）
Zhongfan Jia is an Associate Professor of Chemistry at Flinders University, Australia. He graduated from Fudan University with a PhD in Polymer Chemistry and Physics in 2007, followed by a postdoctoral position in the Centre for Advanced Macromolecular Design (CAMD) at the University of New South Wales. From 2009 to 2020, he was a senior research fellow at the Australian Institute for Bioengineering and Nanotechnology (AIBN), the University of Queensland. He is a recipient of the Australian Research Council Future Fellow and Advanced Queensland Industry Fellow. In 2019, he was appointed as a Lecturer in Chemistry at the University of New England. He joined Flinders University as a Senior Lecturer in 2020 and was promoted to Associate Professor in 2022. His research interests include polymer chemistry, organic electrochemistry, biomaterial, catalysis, and energy storage.
Michelle L. Coote
Professor Michelle Coote is a Georgina Sweet ARC Laureate Fellow and is also an Executive Editor of the Journal of the American Chemical Society. She graduated with a PhD from the University of New South Wales. She established her own research group at the ANU in 2004, where she was promoted to Professor in 2011. She moved to Flinders University as a Matthew Flinders Professor in Chemistry in 2022. She is a member of the new ARC Centre of Excellence for Quantum Biotechnology. Professor Coote is an elected fellow of the Australian Academy of Science (FAA), the Royal Australian Chemical Institute (FRACI) and the Royal Society of Chemistry (FRSC). She has received many awards including the recent HG Smith Medal (2016), the RSC Australasian Lectureship (2020) and Leighton Medal (2021) Her current research spans theoretical and experimental chemistry, in areas as diverse as polymer chemistry, organic synthesis, physical chemistry and organometallic catalysis.
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