Energy storage modification of coal gangue and its application in high-specific-energy batteries
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摘要:
煤矸石电化学储能利用有力地支撑了煤矿产业的能源共生发展，同时解决了矿山固废排放问题，为矿山固体废弃物的资源化利用和推进绿色低碳开采提供了前瞻性的解决方案。通过可控的碱烧活化与酸化学改性技术，将矸石固废转化为纳米级储能材料，实现了其在高比能电池领域的高效应用。采用透射电子显微镜（TEM）、X射线光电子能谱（XPS）等技术，对改性煤矸石和原矸石的微观结构进行了详细表征，旨在深入揭示改性机理。通过单因素试验方法，深入分析了原煤矸石与改性煤矸石在组分、晶体结构及局部电子环境方面的差异，进而确定了改性煤矸石在储能应用中的最佳条件。结果表明：经过改性处理，煤矸石表面形成了一层非晶态纳米颗粒Al2O3活化层，有效降低了电极反应过程中的能量损耗；改性煤矸石表面富含含氧官能团和氧空位等高活性电催化位点，显著降低了表面反应的活化能。在锂−氧气电池中，改性煤矸石展现出较低的充放电过电势（1.12 V）、高放电比容量（
8310 mAh/g）以及优异的续航稳定性（>180 h）；改性煤矸石表现出柔性可穿戴储能特性，在45°翻折状态下仍能稳定供能。对于促进矿山废弃物的资源化利用、降低环境污染、提高资源利用效率等方面具有重要的实践意义和应用价值。Abstract:The electrochemical energy storage utilization of coal gangue robustly supports the synergetic energy development of the coal mining industry, while addressing solid waste disposal issues, offering a forward-looking solution for the resourceful utilization of mining solid waste and the promotion of green and low-carbon mining. Through refined alkali activation and acid chemical modification techniques, this study innovatively transforming gangue waste into high-value-added energy storage materials and realizing their efficient application in the field of high-specific-energy batteries. The microstructure of modified coal gangue and original gangue was characterized in detail using techniques such as transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), aiming to reveal the modification mechanism in depth. Through single factor experimental methods, the differences in composition, crystal structure, and local electronic environment between raw coal gangue and modified coal gangue were analyzed in depth, and the optimal conditions for modified coal gangue in energy storage applications were determined. The results indicate that: After modification treatment, a layer of amorphous nano particle Al2O3 activation layer was formed on the surface of coal gangue, effectively reducing energy loss during the electrode reaction process; The surface of modified coal gangue is rich in highly active electrocatalytic sites such as oxygen-containing functional groups and oxygen vacancies, significantly reducing the activation energy of surface reactions. The modified coal gangue exhibits low overpotentials for charging and discharging (1.12 V), high discharge specific capacity (
8310 mAh/g), and long cycling stability (>180 h) in lithium-oxygen batteries. Modified coal gangue exhibits flexible and wearable energy storage characteristics, and can still provide stable energy supply even when folded at a 45° angle. The study has important practical significance and application value for promoting the resource utilization of mining waste, reducing environmental pollution, and improving resource utilization efficiency. -
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图 2 改性煤矸石微观形貌和结构特征
Figure 2. Micro-morphology and structural characteristics of modified coal gangue
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图 3 改性煤矸石和预处理矸石的XPS
Figure 3. XPS spectra of modified coal gangue and pretreated coal gangue
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图 4 柔性锂−氧气电池组装成品
Figure 4. Finished assembly drawing of flexible lithium oxygen battery
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图 5 首次放电/充电循环后活性煤矸石的Li 1s 和Al 2p XPS光谱
Figure 5. Li 1s and Al 2p XPS spectra of activated coal gangue after the first discharge/charge cycle
表 1 煤矸石XRF测试结果
Table 1 XRF test results of coal gangue
矸石来源 质量分数/% SiO2 Al2O3 Fe2O3 TiO2 MgO K2O Na2O CaO 其他 淮北矿业袁店一井 洗选矸石 59.92 24.67 7.57 0.91 0.67 1.20 0.37 1.08 3.63 掘进矸石 59.46 26.87 7.88 0.96 0.62 1.49 0.50 0.64 1.60 
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