High-performance anode materials based on anthracite for lithium-ion battery applications
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摘要: 以我國資源豐富的低成本優質無煙煤為原料，經過2800 ℃高溫純化、石墨化處理，制備出鋰電池用負極材料，用相同手段處理商業化石墨的前體石油焦與石墨化無煙煤作對比。通過X射線衍射（XRD），掃描電子顯微鏡（SEM），透射電子顯微鏡（TEM），拉曼光譜（Roman）和氮吸附?解吸等手段對無煙煤基負極材料進行微觀結構的表征。采用恒流充放電（GCD），循環伏安（CV）表征其電化學性能。實驗結果表明，無煙煤基石墨化負極材料的石墨化度可達95.44%，比表面積為1.1319 m2·g?1，石墨片層結構平整光滑。該石墨化無煙煤作為鋰離子電池的負極材料首次庫倫效率為87%，在0.1C的電流密度下具有345.3 mA·h·g?1的可逆容量，且在高倍率下該材料比石墨化石油焦材料顯現出更好儲鋰性能，這歸功于石墨化無煙煤較為規則高度有序的表面結構。在不同倍率循環后電流密度恢復到0.1C時容量基本無衰減，100圈循環后可逆容量保持率高達93.8%，基本與石墨化石油焦負極相當，擁有優異的循環穩定性。無煙煤基石墨在容量、倍率性能及循環穩定性上基本接近甚至超過石墨化石油焦。本研究表明，采用優質無煙煤作為原料生產鋰離子電池負極材料具有潛在的研究價值和廣闊的商業前景。Abstract: The rise in the price of petroleum coke and needle coke, which are used as anode materials of lithium-ion batteries, has revealed the difficulty of the industry in finding high-performance and low-cost alternatives of these raw materials. In this study, anthracite, a low-cost, high-quality raw material, of which China is rich in resources, was used. After a 2800 °C purification and graphitization treatment, the anode material for lithium battery was prepared. Petroleum coke, as the precursor of commercial graphite, was treated using the same method that was being used for graphitized anthracite, for comparison reasons. The microstructure of anthracite-based anode materials was characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy (Roman), and nitrogen adsorption-desorption. Cyclic voltammetry (CV) was used to characterize the electrochemical performance of anthracite-based anode materials by applying constant current charge and discharge (GCD). The experimental results show that the graphitization degree of anthracite-based graphitized anode material can reach 95.44%, with the specific surface area being 1.1319 m2·g?1, and the graphite sheet structure is found to be smooth. The graphitized anthracite, as the anode material of a lithium-ion battery, has a first coulombic efficiency of 87% and a reversible capacity of 345.3 mA·h·g?1 at a current rate of 0.1C, and the material has better lithium storage performance than graphitized petroleum coke material at a high rate. The relatively highly ordered surface structure of graphitized anthracite leads to a better storage performance of lithium. When the current rate returns to 0.1C after different current rates, the capacity has basically no attenuation. After 100 cycles, the reversible capacity retention rate is as high as 93.8%, which is basically equivalent to the rate of graphitized petroleum coke anode while the graphitized anthracite also shows excellent cycle stability. Anthracite-based graphite is equivalent or even superior to graphitized petroleum coke in terms of capacity, rate performance, and cycle stability. This study shows that the use of high-quality anthracite as raw material for the production of lithium-ion battery anode materials has a potential research value and broad commercial prospects.
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圖 1 無煙煤和石油焦及其石墨化后的微觀形貌圖。（a）無煙煤前體；（b，c，d）GA樣品掃描電鏡圖；（e）石油焦前體；（f，g，h）GPC樣品掃描電鏡圖
Figure 1. Microscopic topography of anthraciteand petroleum coke after graphitization: (a) anthracite precursor; (b, c, d) GA sample; (e) petroleum coke precursor; (f，g，h) scanning electron micrograph of GPC sample
圖 2 GA樣品透射電鏡圖。（a，b）透射電鏡；（c，d）高倍透射電鏡
Figure 2. Transmission electron micrograph of GA sample: (a, b) TEM; (c, d) HRTEM
圖 5 GA和GPC樣品的吸附曲線及孔徑分布情況。（a）GA的氮氣吸附?解吸等溫線；（b）GA的孔徑分布曲線；（c）GPC的氮氣吸附?解吸等溫線；（d）GPC的孔徑分布曲線
Figure 5. Adsorption curve and pore size distribution of GA and GPC sample: (a) nitrogen adsorption-desorption isotherm of GA; (b) pore size distribution curve of GA; (c) nitrogen adsorption-desorption isotherm of GPC; (d) pore size distribution curve of GPC
圖 6 GA和GPC不同倍率充放電曲線。（a）0.1C～1C倍率下GA的充放電曲線；（b）0.1C～1C倍率下GPC的充放電曲線
Figure 6. Charge and discharge curves of GA and GPC at different magnifications: (a) charge and discharge curves of GA at 0.1C–1C rate; (b) charge and discharge curves of GPC at 0.1C–1C rate
圖 7 GA和GPC的倍率曲線及循環伏安曲線。（a）0.1C～1C倍率下GA和GPC的倍率曲線；（b）GA的循環伏安掃描曲線
Figure 7. Magnification curve and cyclic voltammetry curve of GA and GPC: (a) magnification curve of GA and GPC at 0.1C–1C rate; (b) cyclic voltammetric curve of GA
圖 8 GA和GPC的循環性能和庫倫效率
Figure 8. Cyclic performance and Coulombic efficiency of GA and GPC
表 1 實驗藥品和試劑
Table 1. Experimental samples and reagents
Reagent name Chemical formula Reagent grade Supplier Polyvinylidene fluoride（PVDF） [?CH2?CF2?] Premium grade CALB Co., Ltd. N-methylpyrrolidone（NMP） C5H9NO Electronic grade Shanghai Titan Technology Co., Ltd. Electrolyte LiPF6 Electronic grade BAK Battery Co., Ltd. Acetylene carbon black（Super-P） C Electronic grade Mitsubishi Chemical Co., Ltd. 
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表 2 石墨化無煙煤灼燒數據
Table 2. Graphitized anthracite burning data
Number Net weight of crucible, m1/g Sample quality, m2/g Total mass after burning, m3/g Ash, (m3?m1)·m2?1/% 1 17.1098 1.5137 17.1140 0.277 2 17.0690 1.5553 17.0732 0.270 3 16.7645 1.0415 16.7674 0.278 4 16.9199 1.0513 16.9229 0.275
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表 3 GA和GPC的首次充放電容量和庫倫效率
Table 3. First charge and discharge capacity and coulombic efficiency of GA and GPC
Sample name First discharge capacity/(mA·h·g?1) First charge capacity/(mA·h·g?1) Irreversible capacity/(mA·h·g?1) Coulombic efficiency/% GA 415.4 361.4 54 87 GPC 395.8 346.3 49.5 87.5
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