{"title":"基于统计优化浸出、原位结晶和热分解的零液体排放工艺,使用浓甲酸从报废锂离子电池的废 NCM111 正极材料中回收所有关键金属","authors":"","doi":"10.1016/j.hydromet.2024.106362","DOIUrl":null,"url":null,"abstract":"<div><p>A green chemistry process has been developed to recycle cathode material from end-of-life lithium ion batteries. NCM111 (LiNi<sub>1/3</sub>Co<sub>1/3</sub>Mn<sub>1/3</sub>O<sub>2</sub>) was completely leached with 13 M formic acid to produce two groups of salts with different solubilities: sparingly soluble cobalt, manganese, and nickel (CMN) formates and highly soluble lithium formate. During leaching, CMN formate salts exceeded their solubility limit in the pregnant leach solution (PLS) and crystallized. Mixed CMN formate salts were recovered by filtering the PLS. Lithium was completely recovered by evaporating the filtered PLS then thermally decomposing the lithium formate obtained in air to lithium carbonate. The purity of the lithium carbonate was 98.1 wt%.</p><p>The leaching process was optimized through response surface methodology experiments. The minimum time required to completely leach NCM111 with 13 M formic acid was 30.8 h. Optimum leaching conditions were L/S = 2.81 mL/g (equivalent to S/L = 356 g/L) and <em>T</em> = 95 °C. During leaching, 98% of CMN formate salts exceeded their solubility limit and crystallized from the PLS.</p><p>The recycling process is simple and generates no liquid or solid waste products. The only reagent is 13 M formic acid. The only by-products are water vapour, which can be condensed and reused, and carbon dioxide gas.</p></div>","PeriodicalId":13193,"journal":{"name":"Hydrometallurgy","volume":null,"pages":null},"PeriodicalIF":4.8000,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0304386X24001026/pdfft?md5=b301022844b383c1c0502dc7e5aa2064&pid=1-s2.0-S0304386X24001026-main.pdf","citationCount":"0","resultStr":"{\"title\":\"A zero-liquid discharge process to recover all critical metals from spent NCM111 cathode material of end-of-life lithium-ion batteries: statistically optimized leaching with formic acid and in-situ crystallization\",\"authors\":\"\",\"doi\":\"10.1016/j.hydromet.2024.106362\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>A green chemistry process has been developed to recycle cathode material from end-of-life lithium ion batteries. NCM111 (LiNi<sub>1/3</sub>Co<sub>1/3</sub>Mn<sub>1/3</sub>O<sub>2</sub>) was completely leached with 13 M formic acid to produce two groups of salts with different solubilities: sparingly soluble cobalt, manganese, and nickel (CMN) formates and highly soluble lithium formate. During leaching, CMN formate salts exceeded their solubility limit in the pregnant leach solution (PLS) and crystallized. Mixed CMN formate salts were recovered by filtering the PLS. Lithium was completely recovered by evaporating the filtered PLS then thermally decomposing the lithium formate obtained in air to lithium carbonate. The purity of the lithium carbonate was 98.1 wt%.</p><p>The leaching process was optimized through response surface methodology experiments. The minimum time required to completely leach NCM111 with 13 M formic acid was 30.8 h. Optimum leaching conditions were L/S = 2.81 mL/g (equivalent to S/L = 356 g/L) and <em>T</em> = 95 °C. During leaching, 98% of CMN formate salts exceeded their solubility limit and crystallized from the PLS.</p><p>The recycling process is simple and generates no liquid or solid waste products. The only reagent is 13 M formic acid. 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引用次数: 0
摘要
我们开发了一种绿色化学工艺来回收利用报废锂离子电池的正极材料。NCM111 (LiNi1/3Co1/3Mn1/3O2)用 13 M 甲酸完全浸出,生成两组溶解度不同的盐:稀溶性钴、锰、镍(CMN)甲酸盐和高溶性甲酸锂。在沥滤过程中,CMN 甲酸盐超过了其在孕浸溶液(PLS)中的溶解度极限并结晶。通过过滤孕浸溶液,回收了混合的甲酸枸橼酸盐。通过蒸发过滤后的 PLS,然后在空气中将获得的甲酸锂热分解为碳酸锂,从而完全回收了锂。碳酸锂的纯度为 98.1%。通过响应面方法实验对浸出过程进行了优化。最佳浸出条件为 L/S = 2.81 mL/g(相当于 S/L = 356 g/L)和 T = 95 °C。在浸出过程中,98% 的甲酸 CMN 盐超过了其溶解极限,并从 PLS 中结晶出来。唯一的试剂是 13 M 甲酸。唯一的副产品是水蒸气(可以冷凝和再利用)和二氧化碳气体。
A zero-liquid discharge process to recover all critical metals from spent NCM111 cathode material of end-of-life lithium-ion batteries: statistically optimized leaching with formic acid and in-situ crystallization
A green chemistry process has been developed to recycle cathode material from end-of-life lithium ion batteries. NCM111 (LiNi1/3Co1/3Mn1/3O2) was completely leached with 13 M formic acid to produce two groups of salts with different solubilities: sparingly soluble cobalt, manganese, and nickel (CMN) formates and highly soluble lithium formate. During leaching, CMN formate salts exceeded their solubility limit in the pregnant leach solution (PLS) and crystallized. Mixed CMN formate salts were recovered by filtering the PLS. Lithium was completely recovered by evaporating the filtered PLS then thermally decomposing the lithium formate obtained in air to lithium carbonate. The purity of the lithium carbonate was 98.1 wt%.
The leaching process was optimized through response surface methodology experiments. The minimum time required to completely leach NCM111 with 13 M formic acid was 30.8 h. Optimum leaching conditions were L/S = 2.81 mL/g (equivalent to S/L = 356 g/L) and T = 95 °C. During leaching, 98% of CMN formate salts exceeded their solubility limit and crystallized from the PLS.
The recycling process is simple and generates no liquid or solid waste products. The only reagent is 13 M formic acid. The only by-products are water vapour, which can be condensed and reused, and carbon dioxide gas.
期刊介绍:
Hydrometallurgy aims to compile studies on novel processes, process design, chemistry, modelling, control, economics and interfaces between unit operations, and to provide a forum for discussions on case histories and operational difficulties.
Topics covered include: leaching of metal values by chemical reagents or bacterial action at ambient or elevated pressures and temperatures; separation of solids from leach liquors; removal of impurities and recovery of metal values by precipitation, ion exchange, solvent extraction, gaseous reduction, cementation, electro-winning and electro-refining; pre-treatment of ores by roasting or chemical treatments such as halogenation or reduction; recycling of reagents and treatment of effluents.