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摘要:
我国微晶石墨（隐晶质石墨）因为品位高、质量好的优势一直在国际微晶石墨市场中占有重要地位。然而由于长期理论研究和资金投入的欠缺使我国微晶石墨深加工技术在相关领域还存在空白，导致国内大部分石墨矿企业还停留在对微晶石墨原矿直接利用或将原矿初加工成低附加值产品进行出售的阶段。近年来微晶石墨在锂离子电池负极材料和各向同性石墨材料等领域的应用潜力受到越来越多的关注。因而如何保护和科学利用微晶石墨这种宝贵的资源成为当下亟需解决的问题。以石墨的结构、性质及资源分布为起点，回顾了微晶石墨各类提纯方法的原理及特点，概述了各类提纯方法的研究状况。此外，还介绍了微晶石墨在锂离子电池负极材料和各向同性石墨材料应用上的研究，最后指出对微晶石墨的提纯和改性处理是实现微晶石墨深加工制备高附加值产品的关键。
Abstract:China's microcrystalline graphite has been occupying an important position in the international microcrystalline graphite market because of the advantages of high grade and good quality. However, due to the lack of long−term theoretical research and capital investment, China's microcrystalline graphite deep−processing technology in the relevant fields is still relatively blank, which leads to most of the domestic graphite mining company still stays in the microcrystalline graphite ore direct utilization or primary processing of raw ore into low value−added products for sale stage. And in recent years, microcrystalline graphite in lithium−ion battery anode materials and anisotropic graphite materials and other areas of application potential mining has also made it receive more and more attention. Therefore, how to protect and scientifically utilize microcrystalline graphite as a valuable resource has become an urgent problem to be solved nowadays. Taking the structure, properties and resource distribution of graphite as a starting point, this paper reviews the principles and characteristics of various purification methods of microcrystalline graphite, and outlines the research status of various purification methods. In addition, the research on the application of microcrystalline graphite in anode materials for lithium−ion batteries and isotropic graphite materials is also introduced. Finally, it is pointed out that the purification and modification of microcrystalline graphite is the key to realize the deep processing of microcrystalline graphite to prepare high value−added products.
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表 1 各类石墨提纯方法优缺点比较[1, 18, 23-25]
Table 1. Comparison of the advantages and disadvantages of various graphite purification methods[1, 18, 23-25]
提纯方法 优点 缺点 浮选法 能耗和试剂消耗最少，成本最低 石墨精矿品位只能达到一定范围而很难获得高纯度的产品 高温法 产品质量高，含碳量可达99.995%以上，
无毒无腐蚀，对环境友好须专门设计建造高温炉，设备昂贵，
一次性投资大，运行成本高碱酸法 一次性投资少、产品品位高、工艺适应性强、
设备常规且通用性强需要高温煅烧导致能量消耗大，反应时间长，
设备腐蚀严重，石墨流失量大，废水污染严重氢氟酸法 工艺流程简单、产品品位高、成本相对较低、
对石墨产品性能影响小氢氟酸有剧毒和强腐蚀性，在使用过程中必须采取严格的
安全保护措施，会产生难处理废水导致环保投入大氯化焙烧法 焙烧温度较低使得能量消耗较高温法小；
具有高的提纯效率和回收率氯气具有毒性和腐蚀性导致对设备操作要求高，
产生难处理废气污染环境
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表 2 主要杂质元素的氧化物及对应氯化物的熔沸点[1]
Table 2. Melting and boiling points of oxides of major impurity elements and corresponding chlorides[1]
杂质元素 对应杂质 熔点/℃ 沸点/℃ Si SiO2 1723 2230 SiCl4 −70 57.6 Al Al2O3 2050 2980 AlCl3 192.6 181.1 Fe Fe2O3 1565 3414 FeCl3 306 315 Ca CaO 2572 2580 CaCl2 782 1600 Mg MgO 2800 3600 MgCl2 712 1412
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