High-performance anode materials based on anthracite for lithium-ion battery applications
-
摘要: 以我国资源丰富的低成本优质无烟煤为原料，经过2800 ℃高温纯化、石墨化处理，制备出锂电池用负极材料，用相同手段处理商业化石墨的前体石油焦与石墨化无烟煤作对比。通过X射线衍射（XRD），扫描电子显微镜（SEM），透射电子显微镜（TEM），拉曼光谱（Roman）和氮吸附−解吸等手段对无烟煤基负极材料进行微观结构的表征。采用恒流充放电（GCD），循环伏安（CV）表征其电化学性能。实验结果表明，无烟煤基石墨化负极材料的石墨化度可达95.44%，比表面积为1.1319 m2·g−1，石墨片层结构平整光滑。该石墨化无烟煤作为锂离子电池的负极材料首次库伦效率为87%，在0.1C的电流密度下具有345.3 mA·h·g−1的可逆容量，且在高倍率下该材料比石墨化石油焦材料显现出更好储锂性能，这归功于石墨化无烟煤较为规则高度有序的表面结构。在不同倍率循环后电流密度恢复到0.1C时容量基本无衰减，100圈循环后可逆容量保持率高达93.8%，基本与石墨化石油焦负极相当，拥有优异的循环稳定性。无烟煤基石墨在容量、倍率性能及循环稳定性上基本接近甚至超过石墨化石油焦。本研究表明，采用优质无烟煤作为原料生产锂离子电池负极材料具有潜在的研究价值和广阔的商业前景。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.
-
图 1 无烟煤和石油焦及其石墨化后的微观形貌图。（a）无烟煤前体；（b，c，d）GA样品扫描电镜图；（e）石油焦前体；（f，g，h）GPC样品扫描电镜图
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
图 2 GA样品透射电镜图。（a，b）透射电镜；（c，d）高倍透射电镜
Figure 2. Transmission electron micrograph of GA sample: (a, b) TEM; (c, d) HRTEM
图 5 GA和GPC样品的吸附曲线及孔径分布情况。（a）GA的氮气吸附−解吸等温线；（b）GA的孔径分布曲线；（c）GPC的氮气吸附−解吸等温线；（d）GPC的孔径分布曲线
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
图 6 GA和GPC不同倍率充放电曲线。（a）0.1C～1C倍率下GA的充放电曲线；（b）0.1C～1C倍率下GPC的充放电曲线
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
图 7 GA和GPC的倍率曲线及循环伏安曲线。（a）0.1C～1C倍率下GA和GPC的倍率曲线；（b）GA的循环伏安扫描曲线
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
图 8 GA和GPC的循环性能和库伦效率
Figure 8. Cyclic performance and Coulombic efficiency of GA and GPC
表 1 实验药品和试剂
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. 
下载: 导出CSV
表 2 石墨化无烟煤灼烧数据
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
下载: 导出CSV
表 3 GA和GPC的首次充放电容量和库伦效率
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
下载: 导出CSV
-
[1] Griffiths G. Review of developments in lithium secondary battery technology. Underwater Technol, 2016, 33(3): 153 doi: 10.3723/ut.33.153 [2] Mekonnen Y, Sundararajan A, Sarwat A I. A review of cathode and anode materials for lithium-ion batteries//SoutheastCon 2016. Norfolk, 2016: 1 [3] Nitta N, Wu F X, Lee J T, et al. Li-ion battery materials: present and future. Mater Today, 2015, 18(5): 252 doi: 10.1016/j.mattod.2014.10.040 [4] Mahmood N, Tang T Y, Hou Y L. Nanostructured anode materials for lithium ion batteries: progress, challenge and perspective. Adv Energy Mater, 2016, 6(17): 1600374 doi: 10.1002/aenm.201600374 [5] Kim Y J, Yang H, Yoon S H, et al. Anthracite as a candidate for lithium ion battery anode. J Power Sources, 2003, 113(1): 157 doi: 10.1016/S0378-7753(02)00528-1 [6] Cameán I, Lavela P, Tirado J L, et al. On the electrochemical performance of anthracite-based graphite materials as anodes in lithium-ion batteries. Fuel, 2010, 89(5): 986 doi: 10.1016/j.fuel.2009.06.034 [7] Zhou X Y, Ma L L, Yang J, et al. Properties of graphitized boron-doped coal-based coke powders as anode for lithium-ion batteries. J Electroanal Chem, 2013, 698: 39 doi: 10.1016/j.jelechem.2013.03.019 [8] Xing B L, Zhang C T, Cao Y J, et al. Preparation of synthetic graphite from bituminous coal as anode materials for high performance lithium-ion batteries. Fuel Process Technol, 2018, 172: 162 doi: 10.1016/j.fuproc.2017.12.018 [9] Xiao J, Li F C, Zhong Q F, et al. Effect of high-temperature pyrolysis on the structure and properties of coal and petroleum coke. J Anal Appl Pyrol, 2016, 117: 64 doi: 10.1016/j.jaap.2015.12.015 [10] Liu X X, Luo J, Zhu Y T, et al. Removal of methylene blue from aqueous solutions by an adsorbent based on metal-organic framework and polyoxometalate. J Alloys Compd, 2015, 648: 986 doi: 10.1016/j.jallcom.2015.07.065 [11] Tian B, Li P F, Li D W, et al. Preparation of micro-porous monolithic activated carbon from anthracite coal using coal tar pitch as binder. J Porous Mater, 2017, 25(4): 1 [12] Wu X, Yang X L, Zhang F, et al. Carbon-coated isotropic natural graphite spheres as anode material for lithium-ion batteries. Ceram Int, 2017, 43(12): 9458 doi: 10.1016/j.ceramint.2017.04.123 [13] Högström K C, Malmgren S, Hahlin M, et al. The buried carbon/solid electrolyte interphase in Li-ion batteries studied by hard X-ray photoelectron spectroscopy. Electrochim Acta, 2014, 138: 430 doi: 10.1016/j.electacta.2014.06.129 [14] Ramos A, Cameán I, Cuesta N, et al. Graphitized stacked-cup carbon nanofibers as anode materials for lithium-ion batteries. Electrochim Acta, 2014, 146: 769 doi: 10.1016/j.electacta.2014.09.035 [15] Tian M, Wang W, Liu Y, et al. A three-dimensional carbon nano-network for high performance lithium ion batteries. Nano Energy, 2015, 11: 500 doi: 10.1016/j.nanoen.2014.11.006 [16] Verma P, Maire P, Novák P. A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries. Electrochim Acta, 2010, 55(22): 6332 doi: 10.1016/j.electacta.2010.05.072 [17] Jung K N, Pyun S I. Effect of pore structure on anomalous behaviour of the lithium intercalation into porous V2O5 film electrode using fractal geometry concept. Electrochim Acta, 2006, 51(13): 2646 doi: 10.1016/j.electacta.2005.08.008 [18] Cameán I, Garcia A B. Graphite materials prepared by HTT of unburned carbon from coal combustion fly ashes: Performance as anodes in lithium-ion batteries. J Power Sources, 2011, 196(10): 4816 doi: 10.1016/j.jpowsour.2011.01.041 [19] Wang C, Zhao H, Wang J, et al. Electrochemical performance of modified artificial graphite as anode material for lithium ion batteries. Ionics, 2013, 19(2): 221 -
点击查看大图
计量
- 文章访问数: 646
- HTML全文浏览量: 404
- PDF下载量: 20
- 被引次数: 0
