锂循环产业链中锂分析方法进展

A Review on Analytical Methods of Lithium in Lithium Industry Cycle

锂资源勘查采冶、锂化合物生产、锂终端产品生产、锂回收和废物处理处置构成了锂循环产业链。该产业链中,锂资源勘查目前可开发利用的锂矿床主要有盐湖卤水型、伟晶岩型、黏土型、锂沸石型、其他卤水型(包括油气田卤水亚类和地热卤水亚类)和离子吸附型6种类型。锂化合物生产主要包括氯化锂、氢氧化锂和碳酸锂等产品,锂终端产品生产主要包括锂电池、玻璃或陶瓷、医药、锂同位素等制品。锂回收主要是从动力锂电池中回收锂元素,其他暂时不可用或成本过高的物料按照废物进行处理处置。就锂循环产业链中锂分析涉及的17种主要分析方法进行汇总及进展评述,根据其原理分为湿法化学分析、分子及原子光谱分析、质谱分析及原位分析四类。湿法化学分析包括重量法、气体体积法、滴定法、电离子选择性电极法、离子色谱法,常用于合金、纯物质、卤水、地热水、医药相关等液体样品常量至痕量锂的含量检测。分子及原子光谱分析包括分光光度法、荧光分光光度法、原子吸收分光光度法、辉光放电质谱法、激光击穿诱导光谱法、电感耦合等离子体发射光谱法,可用于锂资源样品、矿冶提取过程产物等常量至痕量锂的测定,其中荧光分光光度法除了用于传统的能源领域,在医疗生物领域同样应用广泛;随着便携式仪器的开发,液体辉光放电光谱法、激光击穿诱导光谱法有望开发专用的快速鉴定装置和方法,为锂资源勘探提供更多的现场分析手段。质谱分析法包括电感耦合等离子体质谱法和热电离质谱法,不仅可以满足锂循环产业链中各类产品中微量至痕量杂质元素含量检测,也可以实现其中锂同位素的测定。原位分析方法包括原位比色法、激光剥蚀多接收等离子体质谱法和二次离子质谱法,近年来在锂产业循环中引起了关注,可分析电池中锂元素分布及迁移,也可对锂矿资源、合金材料等进行分析获得痕量元素的离子图谱、同位素信息及更多的固体表面信息。以上17种分析方法覆盖了锂循环全产业链的绝大多数分析需求,应用过程中可根据样品特征、研究需求的不同进行选择。

Lithium resource exploration,mining and extraction,lithium compound production,lithium terminal product production,lithium recovery and waste disposal constitute the lithium cycle industry chain.In this industry chain,lithium resource exploration has six types of lithium deposits:salt lake lithium brines,lithium pegmatites,lithium−clays,lithium−zeolites,oil−gas field lithium brines or geothermal lithium brines,and ion-absorption lithium.Lithium end products mainly include lithium batteries,glass or ceramics,pharmaceuticals,lithium isotopes and other products.Lithium recovery mainly refers to the recovery of lithium from power lithium batteries.Other materials that are temporarily unavailable or too expensive are treated as waste.This paper summarized and reviewed the progress of 17 main analytical methods involved in the analysis of lithium in the lithium recycling industry chain.According to their principles,they are divided into four categories:wet chemical analysis,molecular and atomic spectroscopy analysis,mass spectrometry analysis and in situ analysis.Wet chemical analysis includes gravimetric,gas volume method,titration,ion selective electrode method and ion chromatography which commonly used for the detection of constant to trace lithium content in liquid samples such as alloys,pure substances,brine,geothermal water and medicine related.Molecular and atomic spectroscopic analysis includes spectrophotometry,fluorescence spectrophotometry,atomic absorption spectrophotometry,glow-discharge mass spectrometry,laser breakdown induction spectrometry,and inductively coupled plasma emission spectrometry.It can be used for the determination of constant to trace amounts of lithium resource samples,mining and smelting process products,etc.,in which fluorescence spectrophotometry is not only used in the traditional energy field,but also widely used in the medical and biological field.With the development of portable instruments,liquid glow-discharge spectroscopy and laser breakdown induction spectroscopy are expected to develop special rapid identification devices and methods,and provide more on-site analysis methods for lithium resource exploration.Mass spectrometry includes inductively coupled plasma mass spectrometry and thermal ionization mass spectrometry,which can not only meet the detection of trace impurity elements in all kinds of products in the lithium cycle industry,but also can get the results of lithium isotopes.In situ methods include in situ colorimetry,Laser ablationmultiple collector-inductively coupled plasma mass spectrometry and secondary ionization mass spectrometry,which have attracted attention in the lithium cycle industry in recent years.They can analyze the distribution and migration of lithium elements in batteries,and can also analyze lithium ore resources and alloy materials to obtain ion maps,isotope information of trace elements and more solid surface information.The above 17 analytical methods cover most the analytical needs of the whole industry chain of lithium cycle,and can be selected according to the different sample characteristics and research needs in the application process.