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废旧三元锂电池正极活性材料中有机成分的热还原效应研究

Study on the thermal reduction effect of organic components in spent ternary lithium battery cathode active materials.

作者信息

Jiang Haidi, Li Zhaohui, Xie Weining, Zhang Guangwen, Yu Zhaoyi, Lu Qichang, He Yaqun

机构信息

School of Chemical Engineering and Technology, China University of Mining &Technology, Xuzhou, Jiangsu 221116, China.

School of Chemical Engineering and Technology, China University of Mining &Technology, Xuzhou, Jiangsu 221116, China; Advanced Analysis and Computation Center, China University of Mining and Technology, Xuzhou, Jiangsu 221116, China.

出版信息

Waste Manag. 2022 Jul 1;148:33-42. doi: 10.1016/j.wasman.2022.05.011. Epub 2022 May 31.

Abstract

To improve the adhesion between cathode materials and current collector, and increase the electronic conductivity among electroactive substances, a certain proportion of conductive agents (acetylene black) and agglomerant (PVDF) are usually added in the battery manufacturing process. However, these conductive agents have negative effects on the recovery of cathode materials by pyrolysis or calcination. Recognizing this issue, a method based on the concept of "treating spent with spent" was developed in this paper. Organic matters contained in cathode active materials functioned as the reduction reagents, which can reduce the valence state of transition metals, resulting in the breakdown of the strong chemical bond and the stable layered structure of cathode materials. In this study, the thermal reduction effect of different organic components on cathode active materials was analyzed respectively to evaluate the reduction function of each component. XRD, XPS and ICP-MS were used to compare and analyze changes of phase, element compound state and ion leaching efficiencies of different cathode materials before and after thermal reduction under different amounts of reducing agents. The results show that both PVDF and acetylene black reduced the high-valent metals to low-valent oxides or elemental substances, demonstrating their thermal reduction capabilities. Comparisons of the XRD, XPS analysis and ion leaching results of thermal reduced products suggest that acetylene black has a stronger thermal reduction ability than that of PVDF. The results also show that the reduction of the high nickel cathode material (NCM811) is easier than that of the low nickel cathode material (NCM111).

摘要

为了提高正极材料与集流体之间的附着力,并增加电活性物质之间的电子导电性,通常在电池制造过程中添加一定比例的导电剂(乙炔黑)和粘结剂(聚偏氟乙烯)。然而,这些导电剂对通过热解或煅烧回收正极材料有负面影响。认识到这一问题,本文提出了一种基于“以废治废”理念的方法。正极活性材料中含有的有机物充当还原剂,可降低过渡金属的价态,导致化学键的断裂和正极材料稳定层状结构的破坏。在本研究中,分别分析了不同有机成分对正极活性材料的热还原效果,以评估各成分的还原作用。利用X射线衍射(XRD)、X射线光电子能谱(XPS)和电感耦合等离子体质谱(ICP-MS)对不同正极材料在不同还原剂用量下热还原前后的相、元素化合物状态和离子浸出效率变化进行了比较分析。结果表明,聚偏氟乙烯和乙炔黑均能将高价金属还原为低价氧化物或单质,显示出它们的热还原能力。对热还原产物的XRD、XPS分析和离子浸出结果的比较表明,乙炔黑的热还原能力比聚偏氟乙烯更强。结果还表明,高镍正极材料(NCM811)的还原比低镍正极材料(NCM111)更容易。

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