羰基氧交联法制备沥青基片状碳负极材料及其储钾性能研究

doi:10.11949/0438-1157.20250556

摘要/Abstract

摘要：

煤沥青（CTP）具有含碳量高、廉价易得等优势，是制备碳材料的优质前驱体之一。然而，CTP直接热解会产生高度石墨化的软碳，导致低的储钾容量和动力学。在此，以四氢呋喃萃取后CTP和草酰氯为原料，氯化铝为催化剂，通过傅克酰基化反应合成了羰基化煤沥青（DCTP）；然后，以DCTP为前驱体，氯化钠为模板，利用一步碳化法制备了煤沥青基片状碳材料（PCSs）。探究了碳化温度对PCSs的结构、化学组成及其储钾性能的影响。羰基的引入促使CTP中多环芳烃分子形成三维聚合物网络，阻止了CTP的熔融和有序重排，羰基氧的脱除调变了碳材料的微观结构。当碳化温度为800℃时，制得的PCS₈₀₀具有扩大的碳层间距、丰富的缺陷和微孔结构。电化学测试结果表明，PCS₈₀₀具有高的储钾容量（在0.05 A·g^-1时容量为310.3 mAh·g^-1）、好的倍率性能（在2 A·g^-1时容量为132.8 mAh·g^-1）和优异的循环稳定性（在2 A·g^-1时1000次循环后容量保持率达90.2%，单个循环的容量损失仅为0.0098%）。这一工作为从煤化工副产物制备高性能钾离子电池用负极材料提供了一种可行的方法。

关键词: 动力学, 聚合物, 电化学, 傅克酰基化反应, 羰基化煤沥青, 钾离子电池

Abstract:

Coal tar pitch (CTP) is one of the excellent precursors of carbon materials because of the merits of high carbon content and low cost. Nevertheless, graphitized soft carbon will be formed via direct pyrolysis of CTP, resulting in low potassium storage capacity and sluggish kinetics. Herein, diketone coal tar pitch (DCTP) was synthesized through the Friedel-Crafts acylation by using tetrahydrofuran-extracted CTP and oxalyl chloride as precursors, aluminum chloride as catalyst. Subsequently, pitch-based carbon sheets (PCSs) were prepared via one-step carbonization method by using DCTP as carbon precursor with sodium chloride as template. The effects of carbonization temperature on the structure, chemical composition, and potassium storage performance of PCSs were investigated in details. The introduction of carbonyl groups facilitates the formation of a three-dimensional polymer network from polycyclic aromatic hydrocarbon molecules in CTP, effectively inhibiting the melting and rearrangement of CTP. The removal of carbonyl oxygen tunes the microstructure of carbon materials. The as-prepared PCS₈₀₀ at the carbonization temperature of 800°C features an enlarged carbon layer spacing, abundant defects, and micropores. The electrochemical test results show that PCS₈₀₀ has a high K⁺ storage capacity (310.3 mAh·g^-1 at 0.05 A·g^-1), good rate performance (132.8 mAh·g^-1 at 2 A·g^-1), and excellent cycling stability (a capacity retention of 90.2% after 1000 cycles at 2 A·g^-1with a capacity loss of only 0.0098% per cycle). This work provides a reliable method for the preparation of high-performance anode materials from coal chemical industry by-products for potassium-ion batteries.

Key words: kinetics, polymers, electrochemistry, Friedel-crafts acylation reaction, diketone coal tar pitch, potassium-ion batteries

中图分类号:

O 646

何军, 梅华羽, 郑景辉, 何孝军. 羰基氧交联法制备沥青基片状碳负极材料及其储钾性能研究[J]. 化工学报, DOI: 10.11949/0438-1157.20250556.

Jun HE, Huayu MEI, Jinghui ZHENG, Xiaojun HE. Preparation of pitch-based carbon sheet anode by diketone oxygen-crosslink strategy and its potassium storage properties[J]. CIESC Journal, DOI: 10.11949/0438-1157.20250556.

图/表 13

图1 PCSs的合成示意图(a)和福克酰基化反应机理(b)

Fig. 1 Schematic diagram of the synthesis of PCSs and Friedel-Crafts acylation reaction mechanism (b)

图2 CTP、ECTP和DCTP的FT-IR光谱(a)、XRD图谱(b)、TG/DTG曲线(c)、XPS谱图(e)、C 1s (f)和O 1s (i)高分辨光谱

Fig. 2 FT-IR spectra (a), XRD patterns (b), TG/DTG curves (c), XPS spectra (e), C 1s (f) and O 1s (i) of CTP, ECTP and DCTP

表1 CTP、ECTP和DCTP中的C 1s和O 1s的元素含量和拟合峰面积占比

Table 1 Element Contents and fitted peak area ratio of C 1s and O 1s in CTP， ECTP， and DCTP

Samples		CPT	ECPT	DCPT
C 1s (at.%)		97.12	95.76	87.42
O 1s (at.%)		2.88	4.24	12.58
C 1s (%)	C=C	32.97	47.62	36.36
	C-C	51.97	36.66	52.67
	C-O	3.83	4.48	5.77
	O-C=O	11.23	11.24	19.66
O 1s (%)	C=O	12.75	20.62	30.84
	C-O	44.31	46.09	25.04
	COOH	42.94	33.29	44.12

图3 FESEM图: PCS600 [(a)、(b)], PCS700 [(c)、(d)], PCS800 [(e)、(f)], PCS900 [(g)、(h)]和EPCS800 [(i)、(j)]. PCS800的FESEM图及其对应的EDS图(k)

Fig. 3 FESEM images of PCS600 [(a)、(b)], PCS700 [(c)、(d)], PCS800 [(e)、(f)], PCS900 [(g)、(h)], and EPCS800 [(i)、(j)]. PCS800 and the corresponding EDS mappings (k)

图4 PCS800的TEM图[(a)、(b)]和HR-TEM图(c)；EPCS800的TEM图[(d)、(e)]和HR-TEM图(f)

Fig. 4 TEM [(a)、(b)] and HR-TEM (c) of PCS800; TEM [(d)、(e)] and HR-TEM (f) of PCS800

图5 PCS600、PCS700、PCS800、PCS900和EPCS800的FT-IR光谱(a)、Raman图谱(b)、XRD图谱(c)、Raman图谱拟合结果(d)和XRD图谱（002）峰拟合结果(e)

Fig. 5 FT-IR spectra (a), Raman spectra (b), XRD patterns (c), Raman spectra fitting results (d), and XRD patterns (002) peaks fitting results (e) of PCS600, PCS700, PCS800, PCS900, and EPCS800

图6 PCS600、PCS700、PCS800、PCS900和EPCS800的TG/DTG曲线(a)、N2吸脱附等温线(b)、孔径分布曲线(c)、XPS谱图(d)、C 1s (e)和O 1s (f)高分辨光谱

Fig. 6 TG/DTG curve (a), N2 adsorption/desorption isotherms (b), pore size distribution curve (c),XPS spectra (d), C 1s (e), and O 1s (f) of PCS600, PCS700, PCS800, PCS900, and EPCS800

表2 PCS600、PCS700、PCS800、PCS900和EPCS800的孔结构参数

Table 2 Pore structure parameters of PCS600， PCS700， PCS800， PCS900， and EPCS800

Samples	D_ap(Å)	S_BET(m²·g^-1)	S_mic(m²·g^-1)	V_t(cm³·g^-1)	V_mic(cm³·g^-1)
PCS₆₀₀	83.51	4.73	1.45	0.0099	0.00046
PCS₇₀₀	73.48	6.00	3.02	0.011	0.0015
PCS₈₀₀	28.54	22.41	17.93	0.016	0.0062
PCS₉₀₀	20.43	75.94	60.00	0.043	0.024
EPCS₈₀₀	102.26	3.45	1.95	0.0088	0.00078

图7 样品电化学储钾性能：PCS800 (a)、PCS600 (b)、PCS700 (c)、PCS900 (d)和EPCS800 (e)在0.1 mV·s-1下的CV曲线；在0.05 A·g-1时的初始充放电曲线(f)；在0.05 ~ 5 A·g-1下的倍率性能(g)；在0.2 A·g-1下的循环寿命(h)；样品在2 A·g-1下的循环寿命（初始3个循环为0.05 A·g-1下激活的过程）(i)

Fig. 7 Electrochemical potassium storage performance of the samples: CV curve of PCS800 (a), PCS600 (b), PCS700 (c), PCS900 (d) and EPCS800 (e) at 0.1 mV·s-1; the initial charge and discharge curve at 0.05 A·g-1 (f); rate performance at 0.05 ~ 5 A·g-1 (g); cycle life at 0.2 A·g-1 (h); cycle life at 2 A·g-1 (i) (initial 3 cycles meaning the activation process at 0.05 A·g-1)

表3 PCS800电极与文献报道电极性能的比较

Table 3 Comparison of performance of PCS800 electrode with that reported in literature

Carbon	ICE (%)	Rate performance (mAh·g^-1@A·g^-1)		Cycling performance	Ref.
Carbon	ICE (%)	Low rate	High rate	Cycling performance	Ref.
BC-6 h	65	358@0.05	192@1	179 mAh·g^-1 after 2000 cycles at 1 A·g^-1	[17]
HHCC	61	303@0.02	27@1	/	[30]
NC	55.6	318.8@0.05	58.3@5	119 mAh·g^-1 after 500 cycles at 1 A·g^-1	[31]
VCA-5	/	258@0.028	145@0.56	173 mAh·g^-1 after 300 cycles at 0.14 A·g^-1	[32]
P-N-C-1000	36	191@0.1	60@3	181 mAh·g^-1 after 2000 cycles at 1 A·g^-1	[33]
FEG-CNC-180	46	312.3@0.1	175@2	220 mAh·g^-1 after 1000 cycles at 1 A·g^-1	[34]
NSC-700	26.4	380@0.05	155@2	275 mAh·g^-1 after 200 cycles at 0.05 A·g^-1	[35]
CJR-NS	37	289@0.1	120@5	111 mAh·g^-1 after 1000 cycles at 5 A·g^-1	[36]
DCTP₈₀₀	52	310@0.05	87.1@5	122 mAh·g^-1 after 1000 cycles at 2 A·g^-1	This work

图8 PCS800在0.1–2 mV·s-1范围内的CV曲线(a)；PCS600 (b)、PCS700 (c)、PCS800 (d)、PCS900 (e)和EPCS800 (f)电极的log(i)与log(v)的线性关系；PCS600 (g)、PCS700 (h)、PCS800 (i)、PCS900 (j)和EPCS800 (k)在2 mV·s-1时电容和扩散过程贡献；电极的电容和扩散过程的贡献(l)

Fig. 8 CV curve of PCS800 in the range of 0.1–2 mV·s-1 (a); Linear relationship between log(i) vs. log(v) of PCS600 (b), PCS700 (c), PCS800 (d), PCS900 (e), and EPCS800 (f) electrode; Capacitance and diffusion control contributions of PCS600 (g), PCS700 (h), PCS800 (i), PCS900 (j), and EPCS800 (k) at 2 mV·s-1; The contribution of the capacitance and diffusion process of the electrodes (l)

图9 电极的Nyquist曲线(a)和ω-1/2与Z′的线性拟合(b)

Fig. 9 Nyquist curves (a) and linear fitting of ω-1/2 to Z' (b)

图10 EXTP和DCTP衍生碳材料结构演变机制及其作用储钾能力示意图

Fig. 10 Schematic diagram of the structural evolution mechanism of ECTP and DCTP-derived carbon materials and their effects on potassium storage capacity

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