Kun Wang , Guoquan Zhang , Mingzhi Luo , Miao Zeng
{"title":"用Cyanex272分离废锂离子电池乙酸浸出液中的Co和Mn","authors":"Kun Wang , Guoquan Zhang , Mingzhi Luo , Miao Zeng","doi":"10.1016/j.jece.2022.108250","DOIUrl":null,"url":null,"abstract":"<div><p><span>Spent lithium-ion batteries (LIBs) contain large amounts of scarce metals, such as Li, Co, Al, Ni, and Mn, and are precious secondary resources. The leaching of spent LIBs using organic acids is considered to be an effective and feasible method for recovering these metals. However, the separation of Li, Co, Ni, and Mn in a solution is difficult to achieve. Using an extractant consisting of 15 % Cyanex272, 10 % tributyl phosphate, and 75 % sulfonated kerosene (v/v) and an organic to aqueous phase ratio of 1:1, over 90.13 % of Al, 95.72 % of Co, and 98.93 % of Mn were extracted. Only 2.05 % of Li and 2.68 % of Ni were co-extracted. The slope method and infrared spectra<span> analysis showed that the extraction processes of Al, Co, and Mn with Cyanex272 follow cationic exchange mechanisms; the acetate anions introduced during the leaching participated in the extraction mechanism of Co. The thermodynamic parameters of Gibb’s free energy, enthalpy change, and entropy change for the extraction reactions were all lower than zero, indicating that the extraction reactions are exothermic and spontaneous and increase the disorder. After washing with NH</span></span><sub>4</sub>HSO<sub>4</sub> 1 M, most of the Co and Mn were removed, and a negligible amount of Al was lost. By adding 2.5 times the stoichiometric amount of (NH<sub>4</sub>)<sub>2</sub>S<sub>2</sub>O<sub>8</sub> to the washing solution and heating at 363.15 K for 40 min, 99.3 % of the Mn was precipitated as MnO<sub>2</sub> with a purity of 96.73 %. After removing Mn, Co<sup>2+</sup> was precipitated as CoC<sub>2</sub>O<sub>4</sub>·2 H<sub>2</sub><span>O using anhydrous oxalic acid; Co</span><sub>3</sub>O<sub>4</sub><span> with a purity of 98.13 % was subsequently obtained by calcination. This study demonstrates the potential of hydrometallurgical processes for the treatment of spent LIBs and provides insights into strategies for the utilization of secondary resources.</span></p></div>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":4.4000,"publicationDate":"2022-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"11","resultStr":"{\"title\":\"Separation of Co and Mn from acetic acid leaching solution of spent lithium-ion battery by Cyanex272\",\"authors\":\"Kun Wang , Guoquan Zhang , Mingzhi Luo , Miao Zeng\",\"doi\":\"10.1016/j.jece.2022.108250\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p><span>Spent lithium-ion batteries (LIBs) contain large amounts of scarce metals, such as Li, Co, Al, Ni, and Mn, and are precious secondary resources. The leaching of spent LIBs using organic acids is considered to be an effective and feasible method for recovering these metals. However, the separation of Li, Co, Ni, and Mn in a solution is difficult to achieve. Using an extractant consisting of 15 % Cyanex272, 10 % tributyl phosphate, and 75 % sulfonated kerosene (v/v) and an organic to aqueous phase ratio of 1:1, over 90.13 % of Al, 95.72 % of Co, and 98.93 % of Mn were extracted. Only 2.05 % of Li and 2.68 % of Ni were co-extracted. The slope method and infrared spectra<span> analysis showed that the extraction processes of Al, Co, and Mn with Cyanex272 follow cationic exchange mechanisms; the acetate anions introduced during the leaching participated in the extraction mechanism of Co. The thermodynamic parameters of Gibb’s free energy, enthalpy change, and entropy change for the extraction reactions were all lower than zero, indicating that the extraction reactions are exothermic and spontaneous and increase the disorder. After washing with NH</span></span><sub>4</sub>HSO<sub>4</sub> 1 M, most of the Co and Mn were removed, and a negligible amount of Al was lost. By adding 2.5 times the stoichiometric amount of (NH<sub>4</sub>)<sub>2</sub>S<sub>2</sub>O<sub>8</sub> to the washing solution and heating at 363.15 K for 40 min, 99.3 % of the Mn was precipitated as MnO<sub>2</sub> with a purity of 96.73 %. After removing Mn, Co<sup>2+</sup> was precipitated as CoC<sub>2</sub>O<sub>4</sub>·2 H<sub>2</sub><span>O using anhydrous oxalic acid; Co</span><sub>3</sub>O<sub>4</sub><span> with a purity of 98.13 % was subsequently obtained by calcination. This study demonstrates the potential of hydrometallurgical processes for the treatment of spent LIBs and provides insights into strategies for the utilization of secondary resources.</span></p></div>\",\"PeriodicalId\":7,\"journal\":{\"name\":\"ACS Applied Polymer Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.4000,\"publicationDate\":\"2022-10-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"11\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Applied Polymer Materials\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S221334372201123X\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Applied Polymer Materials","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S221334372201123X","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
Separation of Co and Mn from acetic acid leaching solution of spent lithium-ion battery by Cyanex272
Spent lithium-ion batteries (LIBs) contain large amounts of scarce metals, such as Li, Co, Al, Ni, and Mn, and are precious secondary resources. The leaching of spent LIBs using organic acids is considered to be an effective and feasible method for recovering these metals. However, the separation of Li, Co, Ni, and Mn in a solution is difficult to achieve. Using an extractant consisting of 15 % Cyanex272, 10 % tributyl phosphate, and 75 % sulfonated kerosene (v/v) and an organic to aqueous phase ratio of 1:1, over 90.13 % of Al, 95.72 % of Co, and 98.93 % of Mn were extracted. Only 2.05 % of Li and 2.68 % of Ni were co-extracted. The slope method and infrared spectra analysis showed that the extraction processes of Al, Co, and Mn with Cyanex272 follow cationic exchange mechanisms; the acetate anions introduced during the leaching participated in the extraction mechanism of Co. The thermodynamic parameters of Gibb’s free energy, enthalpy change, and entropy change for the extraction reactions were all lower than zero, indicating that the extraction reactions are exothermic and spontaneous and increase the disorder. After washing with NH4HSO4 1 M, most of the Co and Mn were removed, and a negligible amount of Al was lost. By adding 2.5 times the stoichiometric amount of (NH4)2S2O8 to the washing solution and heating at 363.15 K for 40 min, 99.3 % of the Mn was precipitated as MnO2 with a purity of 96.73 %. After removing Mn, Co2+ was precipitated as CoC2O4·2 H2O using anhydrous oxalic acid; Co3O4 with a purity of 98.13 % was subsequently obtained by calcination. This study demonstrates the potential of hydrometallurgical processes for the treatment of spent LIBs and provides insights into strategies for the utilization of secondary resources.
期刊介绍:
ACS Applied Polymer Materials is an interdisciplinary journal publishing original research covering all aspects of engineering, chemistry, physics, and biology relevant to applications of polymers.
The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrates fundamental knowledge in the areas of materials, engineering, physics, bioscience, polymer science and chemistry into important polymer applications. The journal is specifically interested in work that addresses relationships among structure, processing, morphology, chemistry, properties, and function as well as work that provide insights into mechanisms critical to the performance of the polymer for applications.