山西南部霍州矿区新良友矿石炭系11号煤中，锂是否主要赋存于结晶度高的高岭石中？

IF 3.6 2区地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS

Chemical Geology Pub Date : 2025-09-10 DOI:10.1016/j.chemgeo.2025.123050

Yan Wang , Shifeng Dai , Yu Liu , David French , Ian Graham , Ning Wang , Jiawei Feng , Niande Shang , Jintian Zheng , Mengda Yao

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引用次数: 0

摘要

锂（Li）是可充电电池的关键元素，由于向清洁能源的过渡，全球需求正在迅速增加。煤系粘土矿物特别是高岭石是重要的锂储集层。虽然先前的研究强调了锂在低结晶高岭石中的优先富集，但在高结晶高岭石中锂的赋存机制尚不清楚。本研究利用电感耦合等离子体质谱（ICP-MS）、场发射扫描电镜（FE-SEM）、飞行时间二次离子质谱（TOF-SIMS）、高分辨率透射电镜（HRTEM）、x射线粉末衍射（XRD）和分子模拟研究了高结晶高岭石中Li的赋存模式和富集机制。山西南部霍州矿区新良友矿石炭系11号煤层样品中Li含量偏高，原煤平均浓度为86.6 μg/g，煤灰平均浓度为505.5 μg/g。这些数值均显著高于硬煤的全球平均值（12 μg/g）和中国煤的全国平均值（31.8 μg/g），表明Li富集程度显著。相关分析和TOF-SIMS数据表明，Li与高结晶高岭石之间存在很强的关联。分子模拟结果表明，Li似乎存在于由[SiO4]四面体或[AlO6]八面体形成的伪六方腔中，而不会破坏高岭石结构或在层间迁移。序贯化学萃取证实了高岭石中Li的高结构稳定性。这些发现为研究Li在高岭石中的结构结合机理提供了新的视角，为研究煤中Li的赋存状态提供了新的途径。

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Can lithium dominantly occur in kaolinite with a high degree of crystallinity in the Carboniferous No. 11 coal from the Xinliangyou mine, Huozhou mining district, southern Shanxi Province, China?

Lithium (Li) is a critical element for rechargeable batteries, and global demand is rapidly increasing due to the transition to clean energy. Coal-hosted clay minerals, particularly kaolinite, are important reservoirs of Li. While previous studies have emphasized the preferential enrichment of Li in poorly crystalline kaolinite, the mechanisms governing Li occurrence in highly crystalline kaolinite remain unclear. This study investigates the modes of occurrence and enrichment mechanisms of Li in highly crystalline kaolinite using inductively coupled plasma-mass spectrometry (ICP-MS), field emission-scanning electron microscopy (FE-SEM), time-of-flight-secondary ion mass spectrometry (TOF-SIMS), high-resolution transmission electron microscopy (HRTEM), X-ray powder diffraction (XRD), and molecular simulation. Samples from the Carboniferous No. 11 coal seam in the Xinliangyou mine, Huozhou mining district, southern Shanxi Province, China, contain elevated Li concentrations, with average concentrations of 86.6 μg/g in raw coal and 505.5 μg/g in coal ash. These values are significantly higher than both the global average for hard coals (12 μg/g) and the national average for Chinese coals (31.8 μg/g), indicating a notable degree of Li enrichment. Correlation analyses and TOF-SIMS data indicate a strong association between Li and highly crystalline kaolinite. Molecular simulation results suggest that Li appears to reside within pseudo-hexagonal cavities formed by [SiO₄] tetrahedra or [AlO₆] octahedra, without disrupting the kaolinite structure or migrating between layers. Sequential chemical extraction confirmed the high structural stability of Li in kaolinite. These findings offer a new perspective on the structural incorporation mechanism of Li in kaolinite and provide a novel approach for investigating the occurrence of Li in coal.

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来源期刊

Chemical Geology 地学-地球化学与地球物理

CiteScore

7.20

自引率

10.30%

发文量

374

审稿时长

3.6 months

期刊介绍： Chemical Geology is an international journal that publishes original research papers on isotopic and elemental geochemistry, geochronology and cosmochemistry. The Journal focuses on chemical processes in igneous, metamorphic, and sedimentary petrology, low- and high-temperature aqueous solutions, biogeochemistry, the environment and cosmochemistry. Papers that are field, experimentally, or computationally based are appropriate if they are of broad international interest. The Journal generally does not publish papers that are primarily of regional or local interest, or which are primarily focused on remediation and applied geochemistry. The Journal also welcomes innovative papers dealing with significant analytical advances that are of wide interest in the community and extend significantly beyond the scope of what would be included in the methods section of a standard research paper.