Study on sodium storage behavior of hard carbons derived from coal with different grades of metamorphism

doi:10.11949/0438-1157.20210668

Abstract

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

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

CLC Number:

TQ 536.9

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.

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.

Figures/Tables 15

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

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

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

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

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

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

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

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)

Fig.6 TEM images of HM-1400

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

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

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

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

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

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)]

References 34

1	Yabuuchi N, Kubota K, Dahbi M, et al. Research development on sodium-ion batteries[J]. Chemical Reviews, 2014, 114(23): 11636-11682.
2	Zhao C L, Wang Q D, Yao Z P, et al. Rational design of layered oxide materials for sodium-ion batteries[J]. Science, 2020, 370(6517): 708-711.
3	Pu X J, Wang H M, Zhao D, et al. Recent progress in rechargeable sodium-ion batteries: toward high-power applications[J]. Small, 2019, 15(32): 1805427.
4	He Y Z, Xu P, Zhang B, et al. Ultrasmall MnO nanoparticles supported on nitrogen-doped carbon nanotubes as efficient anode materials for sodium ion batteries[J]. ACS Applied Materials & Interfaces, 2017, 9(44): 38401-38408.
5	Li Z, Zhang C Z, Han F, et al. Improving the cycle stability of FeCl₃-graphite intercalation compounds by polar Fe₂O₃ trapping in lithium-ion batteries[J]. Nano Research, 2019, 12(8): 1836-1844.
6	Li Z, Zhang C Z, Han F, et al. Towards high-volumetric performance of Na/Li-ion batteries: a better anode material with molybdenum pentachloride-graphite intercalation compounds (MoCl₅-GICs)[J]. Journal of Materials Chemistry A, 2020, 8(5): 2430-2438.
7	Deng W W, Qian J F, Cao Y L, et al. Graphene-wrapped Na₂C₁₂H₆O₄ nanoflowers as high performance anodes for sodium-ion batteries[J]. Small, 2016, 12(5): 583-587.
8	Fu S D, Ni J F, Xu Y, et al. Hydrogenation driven conductive Na₂Ti₃O₇ nanoarrays as robust binder-free anodes for sodium-ion batteries[J]. Nano Letters, 2016, 16(7): 4544-4551.
9	Sun N, Guan Z R X, Liu Y W, et al. Extended “adsorption-insertion” model: a new insight into the sodium storage mechanism of hard carbons[J]. Advanced Energy Materials, 2019, 9(32): 1901351.
10	Qu W H, Guo Y B, Shen W Z, et al. Using asphaltene supermolecules derived from coal for the preparation of efficient carbon electrodes for supercapacitors[J]. The Journal of Physical Chemistry C, 2016, 120(28): 15105-15113.
11	Qi Y R, Lu Y X, Liu L L, et al. Retarding graphitization of soft carbon precursor: from fusion-state to solid-state carbonization[J]. Energy Storage Materials, 2020, 26: 577-584.
12	陆倩, 徐园园, 木沙江, 等. 不粘煤基活性炭作超级电容器电极材料: 硼、氮掺杂对其电化学性能的影响[J]. 新型炭材料, 2017, 32(5): 442-450.
	Lu Q, Xu Y Y, Mu S J, et al. The effect of nitrogen and/or boron doping on the electrochemical performance of non-caking coal-derived activated carbons for use as supercapacitor electrodes[J]. New Carbon Materials, 2017, 32(5): 442-450.
13	Li Y M, Hu Y S, Qi X G, et al. Advanced sodium-ion batteries using superior low cost pyrolyzed anthracite anode: towards practical applications[J]. Energy Storage Materials, 2016, 5: 191-197.
14	Lu H Y, Sun S F, Xiao L F, et al. High-capacity hard carbon pyrolyzed from subbituminous coal as anode for sodium-ion batteries[J]. ACS Applied Energy Materials, 2019, 2(1): 729-735.
15	Liu X F, Song D Z, He X Q, et al. Insight into the macromolecular structural differences between hard coal and deformed soft coal[J]. Fuel, 2019, 245: 188-197.
16	Xie X, Zhao Y, Qiu P H, et al. Investigation of the relationship between infrared structure and pyrolysis reactivity of coals with different ranks[J]. Fuel, 2018, 216: 521-530.
17	Steel K M, Patrick J W. The production of ultra clean coal by sequential leaching with HF followed by HNO₃[J]. Fuel, 2003, 82(15/16/17): 1917-1920.
18	Mathews J P, Chaffee A L. The molecular representations of coal—a review[J]. Fuel, 2012, 96: 1-14.
19	Wang B Y, Xia J L, Dong X L, et al. Highly purified carbon derived from deashed anthracite for sodium-ion storage with enhanced capacity and rate performance[J]. Energy & Fuels, 2020, 34(12): 16831-16837.
20	Li Q, Wang Z H, He Y, et al. Pyrolysis characteristics and evolution of char structure during pulverized coal pyrolysis in drop tube furnace: influence of temperature[J]. Energy & Fuels, 2017, 31(5): 4799-4807.
21	Wang D C, Jin L J, Wei B Y, et al. Oxidative catalytic cracking and reforming of coal pyrolysis volatiles over NiO[J]. Energy & Fuels, 2020, 34(6): 6928-6937.
22	He X Q, Liu X F, Nie B S, et al. FTIR and Raman spectroscopy characterization of functional groups in various rank coals[J]. Fuel, 2017, 206: 555-563.
23	Zhang S X, Li C R, Huang R, et al. Thermogravimetric study of the kinetics and characteristics of the pyrolysis of pulverized coal[J]. Materials Research Express, 2020, 7(8): 085604.
24	Wang C Y, Xing Y W, Xia Y C, et al. Investigation of interactions between oxygen-containing groups and water molecules on coal surfaces using density functional theory[J]. Fuel, 2021, 287: 119556.
25	Miura K. Mild conversion of coal for producing valuable chemicals[J]. Fuel Processing Technology, 2000, 62(2/3): 119-135.
26	Lu Y X, Zhao C L, Qi X G, et al. Pre-oxidation-tuned microstructures of carbon anodes derived from pitch for enhancing Na storage performance[J]. Advanced Energy Materials, 2018, 8(27): 1800108.
27	Sun D, Luo B, Wang H Y, et al. Engineering the trap effect of residual oxygen atoms and defects in hard carbon anode towards high initial Coulombic efficiency[J]. Nano Energy, 2019, 64: 103937.
28	Sadezky A, Muckenhuber H, Grothe H, et al. Raman microspectroscopy of soot and related carbonaceous materials: spectral analysis and structural information[J]. Carbon, 2005, 43(8): 1731-1742.
29	Li Y M, Mu L Q, Hu Y S, et al. Pitch-derived amorphous carbon as high performance anode for sodium-ion batteries[J]. Energy Storage Materials, 2016, 2: 139-145.
30	Cao Y L, Xiao L F, Sushko M L, et al. Sodium ion insertion in hollow carbon nanowires for battery applications[J]. Nano Letters, 2012, 12(7): 3783-3787.
31	Qi Y R, Lu Y X, Ding F X, et al. Slope-dominated carbon anode with high specific capacity and superior rate capability for high safety Na-ion batteries[J]. Angewandte Chemie International Edition, 2019, 58(13): 4361-4365.
32	Alvin S, Yoon D, Chandra C, et al. Revealing sodium ion storage mechanism in hard carbon[J]. Carbon, 2019, 145: 67-81.
33	Jiang B, Zhang Y, Yan D, et al. Ultrafast sodium storage through capacitive behaviors in carbon nanosheets with enhanced ion transport[J]. ChemElectroChem, 2019, 6(12): 3043-3048.
34	Xia J L, Yan D, Guo L P, et al. Hard carbon nanosheets with uniform ultramicropores and accessible functional groups showing high realistic capacity and superior rate performance for sodium-ion storage[J]. Advanced Materials, 2020, 32(21): 2000447.

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