不同变质程度煤衍生硬炭的储钠行为研究

doi:10.11949/0438-1157.20210668

摘要/Abstract

摘要：

煤具有碳含量高、芳香结构发达、成本低廉等优点，是制备钠离子电池硬炭负极材料的优质前驱体。然而煤种类繁多且含有无机杂质，不同种煤热解成炭后材料的石墨化度、碳层间距和表面化学组成各异，导致煤基硬炭负极的电化学性能优化难以展开。选择四种不同变质程度的煤，采用酸洗脱灰、高温炭化的方法制备了系列煤基硬炭，研究了变质程度、炭化温度对煤基硬炭微晶结构和表面杂原子组成的影响，并考察了其相应的储钠行为。其中，褐煤1400℃炭化得到的硬炭性能最佳，在0.02 A·g^-1电流密度下表现出338.8 mA·h·g^-1的比容量和81.1%的首次库仑效率。优异的电化学性能归因于褐煤硬炭较大的碳层间距和丰富的储钠缺陷位点，提供了高嵌入和吸附储钠容量。

关键词: 电化学, 钠离子电池, 热解, 硬炭, 制备, 褐煤

Abstract:

Coal has the advantages of high carbon content, developed aromatic structure and low cost. It is a high-quality precursor for the preparation of hard carbon anode materials for sodium ion batteries. However, the graphitization degree, carbon layer spacing, and chemical composition of the coal-based hard carbons are different due to the complex structure and the presence of inorganic impurity in the various kinds of coal, which makes it challenging to optimize the electrochemical performance of coal-based hard carbon anodes. Herein, four types of coal with different grades of metamorphism are chosen to prepare a series of coal-based hard carbons by acid elution of ash and high-temperature carbonization treatment. Furthermore, the effects of the metamorphic grade and carbonization temperature on the microcrystalline structure and surface heteroatomic composition of coal-based hard carbon were studied, and the corresponding sodium storage behaviors were investigated as well. Therein, the hard carbon anode derived from lignite carbonized at 1400℃ exhibits the optimum performance, a high capacity of 338.8 mA·h·g^-1 is delivered at a current density of 0.02 A·g^-1and a high initial Coulombic efficiency of 81.1% is displayed. The excellent electrochemical performance can be attributed to the larger carbon layer spacing and rich reversible sodium storage defect sites, which provide more sites for embedding and adsorbing sodium storage.

Key words: electrochemistry, sodium-ion batteries, pyrolysis, hard carbon, preparation, lignite

中图分类号:

TQ 536.9

王博阳, 夏吉利, 董晓玲, 郭行, 李文翠. 不同变质程度煤衍生硬炭的储钠行为研究[J]. 化工学报, 2021, 72(11): 5738-5750.

Boyang WANG, Jili XIA, Xiaoling DONG, Hang GUO, Wencui LI. Study on sodium storage behavior of hard carbons derived from coal with different grades of metamorphism[J]. CIESC Journal, 2021, 72(11): 5738-5750.

图/表 15

表1 不同煤种煤脱灰前后的工业分析与脱灰后的元素分析结果

Table 1 Industrial analysis before and after deashing of different coals and elemental analysis results of coals after deashing

煤种	原煤工业分析/%(质量)			脱灰样工业分析/%(质量)			脱灰样元素分析/%(质量)
煤种	M_ad	A_d	V_daf	M_ad	A_d	V_daf	C	N	H	S	O
无烟煤（WYM）	0.11	10.37	10.23	1.50	1.00	9.70	88.91	0.42	4.04	0.66	5.97
烟煤（YM）	2.32	3.78	30.72	3.20	0.41	28.01	76.01	0.83	4.62	0.60	17.90
次烟煤（CYM）	5.21	4.80	47.51	4.56	0.31	42.62	71.64	0.85	6.01	0.42	21.08
褐煤（HM）	8.45	15.27	49.96	6.71	0.75	44.01	67.83	1.33	5.10	1.10	24.55

表2 原煤和脱灰煤的X射线荧光光谱分析

Table 2 X-Ray fluorescence spectrum analysis results for the raw coals and demineralized coals

组分	原煤XRF分析/%(质量)				脱灰样XRF分析/%(质量)
组分	WYM	YM	CYM	HM	WYM	YM	CYM	HM
SiO₂	4.240	0.320	0.360	7.560	0.180	0.093	0.000	0.011
Al₂O₃	3.790	0.300	0.410	2.440	0.680	0.130	0.000	0.096
Fe₂O₃	0.410	1.210	0.785	0.779	0.040	0.166	0.561	0.221
CaO	0.520	2.690	2.150	0.973	0.060	0.050	0.110	0.010
MgO	0.000	0.360	0.000	0.240	0.000	0.000	0.000	0.000
Cr₂O₃	0.024	0.033	0.000	0.033	0.004	0.000	0.000	0.000
Na₂O	0.110	0.000	0.000	0.280	0.000	0.000	0.000	0.000
CuO	0.009	0.000	0.011	0.013	0.001	0.000	0.000	0.006

图1 原煤(a)和脱灰煤(b)的FT-IR谱图

Fig.1 FT-IR spectra of the raw coals and demineralized coals

图2 不同变质程度脱灰煤的TG、DTG和DSC曲线

Fig.2 TG analysis results of demineralized coals with different rank

图3 不同炭化温度下制备的样品的XRD谱图(a) 无烟煤基硬炭;(b) 烟煤基硬炭;(c) 次烟煤基硬炭;(d) 褐煤基硬炭

Fig.3 XRD patterns of the samples prepared at different carbonization temperatures(a) WYM-based carbons; (b) YM-based carbons; (c) CYM-based carbons; (d) HM coal-based carbons

表3 不同炭化温度下制备的煤基硬炭的结构参数

Table 3 Structural parameters of coal-based hard carbons prepared at different carbonization temperatures

Sample	d₀₀₂/nm	L_c/nm	L_a/nm	A_G/A_D	S_BET/(m²·g^-1)
WYM-1000	0.364	2.43	1.86	0.36	3.66
WYM-1200	0.362	2.59	1.94	0.40	8.06
WYM-1400	0.358	3.10	2.03	0.48	3.00
WYM-1600	0.349	4.03	2.43	0.51	4.32
YM-1000	0.381	2.13	1.75	0.27	4.53
YM-1200	0.374	2.32	1.83	0.29	3.95
YM-1400	0.370	2.46	2.06	0.44	2.63
YM-1600	0.364	2.60	2.13	0.49	1.96
CYM-1000	0.380	2.13	1.77	0.26	5.53
CYM-1200	0.377	2.25	1.80	0.30	9.94
CYM-1400	0.372	2.32	2.09	0.38	2.28
CYM-1600	0.365	2.56	2.18	0.44	2.20
HM-1000	0.384	2.11	1.80	0.21	4.13
HM-1200	0.381	2.20	1.82	0.24	4.24
HM-1400	0.376	2.33	1.98	0.28	3.42
HM-1600	0.368	2.46	2.07	0.40	4.42

图4 不同炭化温度下得到的样品的拉曼光谱图(a) 无烟煤基硬炭; (b) 烟煤基硬炭; (c) 次烟煤基硬炭; (d) 褐煤基硬炭

Fig.4 Raman spectra of the samples prepared at different carbonization temperatures(a) WYM-based carbons; (b) YM-based carbons; (c) CYM-based carbons; (d) HM-based carbons

图5 样品WYM-1000、YM-1400、CYM-1400和HM-1400的氮吸附等温线（WYM-1000、YM-1400和CYM-1400的等温线分别垂直平移15、10和5 cm3·g-1)

Fig.5 Nitrogen sorption isotherms of WYM-1000, YM-1400, CYM-1400 and HM-1400(The isotherm of WYM-1000, YM-1400 and CYM-1400 are vertically offset by 15, 10 and 5 cm3·g-1, respectively)

图6 样品HM-1400的透射电子显微镜图

Fig.6 TEM images of HM-1400

图7 各煤基硬炭作为钠电负极材料在0.02 A·g-1下的首次恒电流放电/充电曲线(a) 无烟煤基硬炭; (b) 烟煤基硬炭; (c) 次烟煤基硬炭; (d) 褐煤基硬炭

Fig.7 The first galvanostatic charge/discharge profiles at 0.02 A·g-1 of each coal-based carbons as anode materials of sodium-ion batteries(a) WYM-based carbons; (b) YM-based carbons; (c) CYM-based carbons; (d) HM coal-based carbons

图8 无烟煤与次烟煤基硬炭(a)、烟煤与褐煤基硬炭(b)在0.02~1 A·g-1电流密度下的倍率性能；煤基硬炭在1 A·g-1电流密度下的循环性能(c)

Fig.8 Rate performance of the samples under the current density ranging from 0.02—1 A·g-1: (a) WYM and CYM-based hard carbons; (b) YM and HM-based hard carbons； (c) Cycle performance of the hard carbons at a current density of 1 A·g-1

图9 YM-1400(a)和HM-1400(c)在0.1~1mV·s-1的不同扫速下的CV曲线；YM-1400(b)和HM-1400(d)在不同扫速下的归一化电容容量贡献占比

Fig.9 CV curves of YM-1400 (a) and HM-1400 (c) at different scan rates from 0.1—1 mV·s-1; Normalized contribution ratio of capacitive capacities of YM-1400 (b) and HM-1400 (d) at different scan rates

图10 YM-1400和HM-1400的C 1s[(a), (b)]和O 1s [(c), (d)]的XPS光谱

Fig.10 XPS spectra of C 1s [(a), (b)] and O 1s [(c), (d)] of YM-1400 and HM-1400

表4 烟煤和褐煤基硬炭的元素分析与XPS分析结果

Table 4 Elemental and XPS analysis results of YM and HM coal-based hard carbons

样品编号	元素分析/%（质量）				XPS分峰C 1s/%		XPS分峰O 1s/%
样品编号	N	C	H	O	sp²C	sp³C	C—O	—OH	CO
YM-1000	1.65	94.47	0.42	3.46	57.43	18.02	5.76	43.82	50.42
YM-1200	1.06	96.23	0.21	2.5	64.04	18.20	5.17	45.60	49.23
YM-1400	0.3	98.06	0.10	1.54	70.62	10.76	4.31	54.13	41.56
YM-1600	0.08	99.09	0.06	0.77	72.01	11.91	1.08	58.71	40.21
HM-1000	1.09	91.42	0.48	7.01	61.74	22.12	30.67	31.21	38.13
HM-1200	0.45	95.69	0.22	3.64	66.05	17.57	14.38	40.06	45.57
HM-1400	0.30	97.74	0.10	1.86	66.54	16.97	10.24	46.86	42.68
HM-1600	0.08	98.63	0.08	1.21	68.37	13.96	0.43	64.85	34.73

图11 YM-1400和HM-1400在充放电过程中的GITT曲线[(a), (b)]; 根据 YM-1400和HM-1400 在放电和充电过程中的GITT电势分布计算出的钠离子扩散系数[(c), (d)]

Fig.11 GITT measurements of YM-1400和HM-1400[(a), （b)]; Sodium-ion apparent diffusion coefficients calculated from the GITT potential profiles of the HM-1400 and YM-1400 electrodes during discharge and charge process[(c), （d)]

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