废旧锂离子电池正极材料资源化回收与再生

随着电子设备的普及和电动汽车行业的迅速崛起,作为提供能量来源的锂离子电池发挥着重要的作用。以钴酸锂、磷酸铁锂以及三元正极材料为代表的锂离子电池产销量不断增加;与此同时,为了提供更长的续航时间以及续航稳定性,新型锂离子电池材料的研究工作也在不断推进。在此背景下,锂离子电池正极材料的失效、废弃以及资源化回收再生的过程就显得愈发重要,如何在下游解决报废锂离子电池处理的问题也逐渐提上日程。基于此,本文分别从湿法和火法再生两个角度对废旧锂离子电池正极材料的回收和再生过程进行了介绍,包括回收条件优化的方法、较为新颖的回收再生方法以及再生材料的性能等,并总结了回收再生过程的杂质元素,包括铝、铜等元素对再生材料结构和性能的影响以及工业上常用的回收废旧锂离子电池的方法和环境影响。最后对锂离子电池回收的方法进行总结并进行展望。     

Modelling of calcium sulphate solubility in concentrated multi-component sulphate solutions

The chemistry of several calcium sulphate systems was successfully modelled in multi-component acid-containing sulphate solutions using the mixed solvent electrolyte (MSE) model for calculating the mean activity coefficients of the electrolyte species. The modelling involved the fitting of binary mean activity, heat capacity and solubility data, as well as ternary solubility data. The developed model was shown to accurately predict the solubility of calcium sulphate from 25 to 95 °C in simulated zinc sulphate processing solutions containing MgSO₄, MnSO₄, Fe₂(SO₄)₃, Na₂SO₄, (NH₄)₂SO₄ and H₂SO₄. The addition of H₂SO₄ results in a significant increase in the calcium sulphate solubility compared to that in water. By increasing the acid concentration, gypsum, which is a metastable phase above 40 °C, dehydrates to anhydrite, and the conversion results in a decrease in the solubility of calcium sulphate. In ZnSO₄–H₂SO₄ solutions, it was found that increasing MgSO₄, Na₂SO₄, Fe₂(SO₄)₃ and (NH₄)₂SO₄ concentrations do not have a pronounced effect on the solubility of calcium sulphate. From a practical perspective, the model is valuable tool for assessing calcium sulphate solubilities over abroad temperature range and for dilute to concentrated multi-component solutions.     

双波长分光光度法测定湿法炼锌净化液中的痕量锗

选择水杨基荧光酮－乳化剂ＯＰ－盐酸为显色体系，应用双波长分光光度法扣除硫酸锌的基体干扰，不分离直接测定了湿法炼锌过程中硫酸锌净化液中的痕量锗。测定范围在０－４０ｍｇ／Ｌ。本法应用于株洲冶炼厂锌净化液中锗的测定，结果与该厂长期的萃取－比色法结果相吻合，而测定速度较萃取－比色法至少提高了一倍。     

离子交换树脂在湿法冶金中的应用

本文简要综述了离子交换树脂在贵金属、稀有金属、稀土金属、铀及其它放射性核素等金属的湿法提取分离与纯化中的应用。     

Quantifying indium with ion chromatography in hydro‐ and biohydrometallurgical leaching solutions

A methodology has been developed to chromatographically quantify indium in polymetallic (bio)hydrometallurgical processing solutions using the Dionex IonPac CS5A column and pyridine‐2,6‐dicarboxylic acid eluent. Cu(II) and In(III) could be separated by elevating the column temperature to 45°C. The comparatively low stability constant of the In‐eluent complex (log K₂ = 3.8) required typical leaching samples to be diluted in the eluent rather than acid or water to overcome ligand competition between components of the sample solution and the eluent. The methodology was applied to leachates from (bio)hydrometallurgical processing of oxidic flue dust residues and sulfidic zinc ores, where both are promising candidates for the recovery of indium from low grade ores and metallurgical wastes. Indium, ferrous iron, ferric iron, copper, zinc, nickel, and manganese concentrations could be simultaneously quantified. The method was found suitable for samples containing at least 0.25 mg/L indium and an iron to indium ratio of up to 100:1.     

重金属湿法冶金过程中钙镁结晶的工业现状及相关相图研究进展

首先介绍湿法冶金和材料制备过程中钙镁结晶危害的工业现状及其对溶液化学和结晶相化学基础研究的要求,然后系统地评述相关体系溶液化学和相化学基础研究的进展.接着在作者的系统工作及文献结果分析基础上指出:钙在重金属硫酸盐体系高温溶解度的实验研究、能描述硫酸盐离子缔合的合理热力学预测模型、硫酸盐水溶液结构的光谱和量子化学研究、以及硫酸盐水溶液高温下水的活度测定等是未来研究工作的重点.这些研究工作将加深对重金属湿法冶金过程中钙镁结晶危害行为及规律的认识,为廉价、环保地避免钙镁结晶危害的新工艺开发奠定了重要基础.     

Benign Recycling of Spent Batteries towards All-Solid-State Lithium Batteries

Lithium-ion batteries (LIBs) are one of the most significant energy storage devices applied in power supply facilities. However, a huge number of spent LIBs would bring harmful resource waste and environmental hazards. In this study, a benign hydrometallurgical method using phytic acid as precipitant is proposed to recover useful metallic Mn ions from spent LiMn₂O₄ batteries. Besides Mn-based cathodes, this recovery process is also applicable for other commercial batteries. More importantly, for the first time, the as-obtained manganous complex is employed as a nanofiller in a polyethylene oxide matrix to largely improve Li⁺ conductivity and transference number. As a result, when applied in all-solid-state lithium batteries, high capacity and outstanding cyclic stability are achieved with capacity retention of 86.4 % after 60 cycles at 0.1 C. The recovery of spent lithium batteries not only has benefits for the environment and resources, but also shows great potential application in all-solid-state lithium batteries, which opens up a costless and efficient circulation pathway for clean and reliable energy storage systems.     

退役三元动力电池回收利用进展

退役三元动力电池中含有大量的钴、锂、镍、锰等高价值金属元素。将退役动力电池进行回收利用,可以有效缓解动力电池退役带来的回收和环境污染压力,从而提高资源利用率和经济效益。本文拟对退役三元动力电池回收利用的国内外技术研究现状进行阐述,着重介绍湿法冶金技术,包括预处理技术和浸出、化学沉淀和溶剂萃取等二次处理技术,并与干法冶金作对比,对其方法及优缺点进行了详细介绍和比较。该研究可以为改进退役三元动力电池回收工艺提供指导,进一步促进工业化的实现。     

我国稀土湿法冶金发展状况及研究进展

介绍了包头混合型稀土精矿、四川氟碳铈矿和南方离子吸附型稀土矿这3类主要稀土工业资源的特点及研究开发的一系列先进稀土冶炼提取工艺技术,并就目前工业上应用的冶炼分离工艺及研究进展进行了综合评述,探讨了我国稀土湿法冶金领域的发展趋势,提出下一步的研究开发方向和重点研究领域为： 稀土矿高效绿色冶炼分离工艺,研究解决三废污染问题,降低单耗和提高资源综合利用率;超高纯及特殊物性的稀土化合物材料制备技术开发,拓展稀土应用领域.     

Solvation of ions,part XXX. Thermodynamics of transfer of copper ions from water to solvent mixtures

Free energies and Walden products show that the Cu⁺ and Ag⁺ ions are specifically solvated by acetonitrile (AN), 2-hydroxycyanoethane (HAN), and by pyridine (Py) whereas Na⁺ is specifically solvated by water, in mixtures of these organics with water. The Cu²⁺ ion is specifically solvated by pyridine in pyridine-water mixtures, but by water in acetonitrile-water mixtures. Ion-solvent, coordinated solvent-bulk solvent, and solvent-solvent interactions produce large entropy losses in the order Cu⁺Ag⁺>Na⁺ for transfer of these ions from water to dilute acetonitrile-water. The metallurgically important oxidations of copper, silver, CuS and Cu₂ with CuSO₄ in water are strongly favored in an enthalpic and free energy sense by the addition of acetonitrile, but addition of acetonitrile also produces a large loss of entropy for the reactions.