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两段式热处理过程中废锂离子电池电解液的转化与归宿。

Conversion and fate of waste Li-ion battery electrolyte in a two-stage thermal treatment process.

机构信息

Department of Solid Waste Treatment and Recycling, Research Center for Eco-environmental Sciences, Chinese Academy of Sciences, 18 Shuangqing Road, Beijing 100085, PR China; University of Chinese Academy of Sciences, Beijing 100049, PR China.

Department of Solid Waste Treatment and Recycling, Research Center for Eco-environmental Sciences, Chinese Academy of Sciences, 18 Shuangqing Road, Beijing 100085, PR China; University of Chinese Academy of Sciences, Beijing 100049, PR China.

出版信息

Waste Manag. 2024 Oct 1;187:1-10. doi: 10.1016/j.wasman.2024.06.027. Epub 2024 Jul 4.

Abstract

Disposal of electrolytes from waste lithium-ion batteries (LIBs) has gained much more attention with the growing application of LIBs, yet handling spent electrolyte is challengeable due to its high toxicity and the lack of established methods. In this study, a novel two-stage thermal process was developed for treating residual electrolytes resulted from spent lithium-ion batteries. The conversion of fluorophosphate and organic matter in oily electrolyte during low-temperature rotation distillation was investigated. The distribution and migration of the concentrated electrolytes were studied and the corresponding reaction mechanisms were elucidated. Additionally, the influence of alkali on the fixation of fluorine and phosphate was further examined. The results indicated that hydrolyzed carbonate esters and lithium in the electrolyte could combine to form LiCO and the hydrolysable hexafluorophosphate was proven to be stable in the concentrated electrolyte (45 rpm/85 °C, 30 min). It was found that CO, CO, CH, and H were the primary pyrolysis gases, while the pyrolysis oil consisted of extremely flammable substances formed by the dissociation and recombination of chemical bonds in the electrolyte solvent. After pyrolysis at 300 °C, fluorine and phosphate were present in the form of sodium fluoride and sodium phosphate. The stability of the residue was enhanced, and the environmental risk was reduced. By adding alkali (KOH/Ca(OH), 20 %), hexafluorophosphate in the electrolyte was transformed into fluoride and phosphate in the residue, thereby reducing the device's corrosion from fluorine-containing gas. This study provides a viable approach for managing the residual electrolyte in the waste lithium battery recovery process.

摘要

处理废锂离子电池(LIB)中的电解质引起了越来越多的关注,随着 LIB 的应用越来越广泛,处理用过的电解质具有挑战性,因为其毒性高且缺乏成熟的方法。在这项研究中,开发了一种处理用过的锂离子电池产生的残余电解质的新型两阶段热工艺。研究了低温旋转蒸馏过程中油性电解质中氟磷酸盐和有机物的转化。研究了浓缩电解质的分布和迁移,并阐明了相应的反应机制。此外,进一步考察了碱对氟和磷固定的影响。结果表明,电解质中的水解碳酸酯和锂可以结合形成 LiCO,并且可水解的六氟磷酸盐在浓缩电解质中是稳定的(45 rpm/85°C,30 min)。发现 CO、CO、CH 和 H 是主要的热解气体,而热解油则由电解质溶剂中化学键的解离和重组形成的极其易燃物质组成。在 300°C 下热解后,氟和磷以氟化钠和磷酸钠的形式存在。残留物的稳定性得到提高,环境风险降低。通过添加碱(KOH/Ca(OH),20%),电解质中的六氟磷酸盐转化为残留物中的氟化物和磷酸盐,从而减少了含氟气体对设备的腐蚀。这项研究为处理废锂离子电池回收过程中的残余电解质提供了一种可行的方法。

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