空气氧化稳定化对沥青基硬炭材料的结构和储钠性能的影响

GUO Hong-yi; LI Yao-yu; WANG Chun-lei; HE Lei; LI Chen; GUO Yong-qiang; ZHOU Ying

doi:10.1016/S1872-5805(21)60075-6

空气氧化稳定化对沥青基硬炭材料的结构和储钠性能的影响

doi: 10.1016/S1872-5805(21)60075-6

大连理工大学化工学院碳素材料研究室，辽宁省能源材料化工重点实验室，辽宁大连 116024

基金项目: 国家自然科学基金（21576047，U1510204，21776040）

详细信息

通讯作者:
周　颖，教授. E-mail: zhouying02@126.com

中图分类号: TQ127.1⁺1
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出版历程
- 收稿日期: 2019-04-12
- 修回日期: 2020-10-11
- 网络出版日期: 2021-11-12
- 刊出日期: 2021-12-01

Effect of the air oxidation stabilization of pitch on the microstructure and sodium storage of hard carbons

Liaoning Key Laboratory of Energy Materials and Chemical Engineering, Carbon Research Laboratory, College of Chemical Engineering, Dalian University of Technology, Dalian 116024, China

Funds: The authors acknowledge the financial support by the National Natural Science Foundation of China, NSFC (21576047, U1510204, 21776040)

More Information

Author Bio:
郭宏毅，硕士研究生. E-mail: guohongyi1993@163.com

Corresponding author: ZHOU Ying, Professor. E-mail: zhouying02@126.com

摘要

摘要: 以石油沥青为原料，通过空气氧化稳定化及炭化方法成功制备出钠离子电池用硬炭负极材料。研究了不同氧化稳定化温度下样品组成、结构的变化，及其对炭化样品形貌、结构和储钠性能的影响。结果表明，空气氧化处理可以引入大量的含氧官能团，诱导脱氢缩合和氧化交联反应的发生，使石油沥青发生由热塑性向热固性的转化。空气氧化稳定化处理有效地阻碍了沥青在高温炭化中固有的石墨化倾向，使碳层堆叠变得无序、同时产生更多的缺陷位。电化学测试结果表明，在100 mA g⁻¹的电流密度下，与直接炭化样品PDC-1400相比，350 ℃氧化稳定化、1400 ℃炭化的硬炭样品o-PDC-350-1400的比容量提升约1.8倍（达到276.8 mAh g⁻¹）；首效提高22%（达到73.38%）。样品o-PDC-350-1400循环200圈后，充电比容量达170.2 mAh g⁻¹，具有良好的循环稳定性。
- 石油沥青 /
- 氧化稳定化 /
- 硬炭 /
- 钠离子电池
Abstract: Hard carbon anode materials for sodium ion batteries were prepared from petroleum pitch by air oxidation stabilization followed by carbonization. The effects of the oxidation stabilization temperature on the compositions and microstructures of the oxidized samples, as well as on the morphology, microstructure and sodium storage property of the carbonized samples were investigated. Results show that air oxidation introduces a large number of oxygen-containing functional groups, induces dehydrogenation condensation and oxidative crosslinking reactions, and transforms the petroleum asphalt from thermoplastic to thermosetting. The air oxidation stabilization treatment effectively hinders the inherent tendency of asphalt to graphitize during high temperature carbonization, resulting in carbons with randomly oriented carbon layers with more defects. Electrochemical tests show that o-PDC-350-1400 (oxidation stabilization at 350 °C, carbonization at 1400 °C) has a high charging specific capacity of 276.8 mAh g⁻¹ at 100 mA g⁻¹ and a high initial coulombic efficiency of 73.38%. Compared with sample PDC-1400 that was directly carbonized at 1400 °C, the charging specific capacity was increased by about 1.8 times and the initial coulombic efficiency was increased by 22%. The charging specific capacity of o-PDC-350-1400 after 200 cycles reached 170.2 mAh g⁻¹, indicating good cycling stability.
- Petroleum asphalt /
- Oxidation stabilization /
- Hard carbon /
- Sodium ion battery

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FIG. 1074. FIG. 1074.

FIG. 1074..

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Figure 1. (a)X-ray diffraction patterns and (b) FT-IR analysis of petroleum asphalt and oxidized petroleum asphalt treated at different oxidation stabilization temperatures.

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Figure 2. (a) XRD patterns and (b) Raman spectra of o-PDC-T-1400 series.

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Figure 3. SEM images of (a) PDC-1400 and (c) o-PDC-350-1400, HRTEM images of (b) PDC-1400 and (d) o-PDC-350-1400 (inserts are the selected area electron diffraction patterns).

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Figure 4. (a) Nitrogen adsorption curves and (b) pore size distributions of PDC-1400 and o-PDC-350-1400.

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Figure 5. (a) Galvanostatic charge/discharge profiles, (b) column charts of slope capacity and platform capacity distribution and (c) rate performance under different current densities of the o-PDC-T-1400 series.

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Figure 6. CV curves of (a) PDC-1400 and (b) o-PDC-350-1400 at a scan rate of 0.1 mV s⁻¹ , (c) cyclic performance of the PDC-1400 and o-PDC-350-1400 under a current density of 30 mA g⁻¹ .

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Table 1. Element analysis, weight gain ratio and carbon yield of samples after oxidation stabilization.

Samples	Elemental composition(%)				C/H	Oxidation weight gain(%)	Yield of carbon(%)
Samples	N	C	H	O*	C/H	Oxidation weight gain(%)	Yield of carbon(%)
Pitch	0.13	94.34	5.02	0.51	1.57	-	53.3
o-P-150	0.25	91.41	5.08	3.26	1.50	0.4	51.8
o-P-200	0.25	88.18	4.7	6.87	1.56	3.3	66.4
o-P-250	0.23	81.32	3.24	15.21	2.09	9.4	72.3
o-P-300	0.25	74.58	2.31	22.86	2.69	6.4	67.0
o-P-350	0.35	70.91	1.32	27.42	4.48	−7.1	61.5
Note: * Calculated by subtraction method

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Table 2. Crystalline parameters of pristine petroleum asphalt and samples after oxidation stabilization.

Samples	F_a	D_m(nm)	D_r(nm)	L_a(nm)	L_c(nm)
Pitch	0.56	0.362	0.549	1.113	0.544
o-P-150	0.54	0.361	0.534	1.154	0.564
o-P-200	0.55	0.358	0.531	1.151	0.563
o-P-250	0.60	0.356	0.535	1.040	0.509
o-P-300	0.60	0.357	0.529	0.903	0.442
o-P-350	0.57	0.356	0.530	0.827	0.405

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Table 3. Crystalline parameters and electrochemical performance of o-PDC-T-1400 series.

Samples	L_c (nm)	L_a (nm)	d₀₀₂(nm)	I_D/I_G	RC (mAh g⁻¹ )	ICE (%)
PDC-1400	3.59	4.739	0.347	0.95	99.6	51.45
o-PDC-150-1400	3.532	4.931	0.347	0.94	99.8	51.92
o-PDC-200-1400	3.484	5.292	0.347	0.95	93.1	48.70
o-PDC-250-1400	1.467	3.292	0.355	1.09	221.3	73.81
o-PDC-300-1400	1.382	3.399	0.356	1.14	230.3	73.02
o-PDC-350-1400	1.313	3.440	0.363	1.20	276.8	73.38

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