乳化/氧化协同制备高倍率钾离子电池负极用沥青基碳微球

doi:10.19799/j.cnki.2095-4239.2022.0765

储能科学与技术 ›› 2023, Vol. 12 ›› Issue (5): 1444-1452.doi: 10.19799/j.cnki.2095-4239.2022.0765

• 喜迎东北大学建校百年-储能电池关键材料与循环技术专刊 • 上一篇下一篇

乳化/氧化协同制备高倍率钾离子电池负极用沥青基碳微球

刘畅¹(), 姚君君¹, 孙颖¹, 冯大明¹, 郑宏杰¹, 马天翼²()

^1.辽宁大学化学院，辽宁沈阳 110000
^2.皇家墨尔本理工大学理学院，澳大利亚墨尔本 3000

收稿日期:2022-12-27 修回日期:2023-01-19 出版日期:2023-05-05 发布日期:2023-05-29
通讯作者: 马天翼 E-mail:liuchang2596@163.com;tianyi.ma@rmit.edu.au
作者简介:刘畅（1988—），男，博士，讲师，主要研究钾离子电池负极材料，E-mail：liuchang2596@163.com；
基金资助:
国家自然科学基金(52071171);辽宁省自然科学基金博士启动项目(2020-BS-081)

Coordinated preparation of pitch-based carbon microspheres for anode materials of high-rate potassium-ion batteries by emulsification/oxidation

Chang LIU¹(), Junjun YAO¹, Ying SUN¹, Daming FENG¹, Hongjie ZHENG¹, Tianyi MA²()

^1.College of Chemistry, Liaoning University, Shenyang 110000, Liaoning, China
^2.School of Science, Royal Melbourne Institute of Technology University, Melbourne, VIC 3000, Australia

Received:2022-12-27 Revised:2023-01-19 Online:2023-05-05 Published:2023-05-29
Contact: Tianyi MA E-mail:liuchang2596@163.com;tianyi.ma@rmit.edu.au

摘要/Abstract

摘要：

在不借助模板的情况下，以中温煤沥青为原料，在表面活性剂和分散介质辅助下，结合预氧化和乳化法成功制备了氧化沥青微球。探究了乳化温度对微球形貌的影响规律，并确定了280 ℃为最佳的乳化温度。制备的氧化沥青碳微球负极展现出良好的电化学性能。在0.05 A/g下的初始放电比容量为310 mAh/g，2 A/g时的容量为102 mAh/g，在1 A/g下经过1000次长循环，容量仍剩余108 mAh/g。其优异的储钾性能得益于低温预氧化形成的交联结构可以实现有序到无序的结构演变。此外，引入的含氧基团不仅使前驱体实现空间层面的交联，确保了材料在电化学脱嵌时的结构稳定性，而且还产生了丰富的空位和缺陷，从而增加储钾位点。

关键词: 煤沥青, 碳材料, 钾离子电池, 负极

Abstract:

In this study, pitch-based carbon microspheres were successfully obtained by using a coordinated emulsification and oxidation method with coal tar pitch as the precursor and assisted by surfactant and dispersion medium without a template. The influence of emulsification temperature on the morphology of microspheres was explored, and the optimal temperature was determined to be 280 ℃. The prepared pitch-based carbon microspheres present excellent electrochemical performance with an initial discharge capacity of 310 mAh/g at 0.05 A/g and 102 mAh/g at 2 A/g. Their long-term cyclability was at 108 mAh/g after 1000 cycles at 1 A/g.The excellent potassium storage performance was because the cross-linking structure formed by low-temperature pre-oxidation can realize the structural evolution from order to disorder. In addition, the introduced oxygen-containing groups promoted crosslinking of precursor molecules at the spatial level, ensuring structural stability during electrochemical de-/intercalation. Nevertheless, they produced abundant vacancies and defects, thereby increasing potassium storage sites.

Key words: coal tar pitch, carbon materials, potassium ion batteries, anode

中图分类号:

TQ 536

刘畅, 姚君君, 孙颖, 冯大明, 郑宏杰, 马天翼. 乳化/氧化协同制备高倍率钾离子电池负极用沥青基碳微球[J]. 储能科学与技术, 2023, 12(5): 1444-1452.

Chang LIU, Junjun YAO, Ying SUN, Daming FENG, Hongjie ZHENG, Tianyi MA. Coordinated preparation of pitch-based carbon microspheres for anode materials of high-rate potassium-ion batteries by emulsification/oxidation[J]. Energy Storage Science and Technology, 2023, 12(5): 1444-1452.

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参考文献 28

1	LIN C R, WANG Y J, ZHONG F L, et al. Carbon materials for high-performance potassium-ion energy-storage devices[J]. Chemical Engineering Journal, 2021, 407: 126991.
2	张贺贺, 孙旦, 王海燕, 等. 钾离子电池负极材料研究进展[J]. 储能科学与技术, 2020, 9(1): 25-39.
	ZHANG H H, SUN D, WANG H Y, et al. Current studies of anode materials for potassium-ion battery[J]. Energy Storage Science and Technology, 2020, 9(1): 25-39.
3	WU Y M, ZHAO H T, WU Z G, et al. Rational design of carbon materials as anodes for potassium-ion batteries[J]. Energy Storage Materials, 2021, 34: 483-507.
4	ZHAO J, ZOU X X, ZHU Y J, et al. Electrochemical intercalation of potassium into graphite[J]. Advanced Functional Materials, 2016, 26(44): 8103-8110.
5	YU K, LIU C, WANG Y, et al. Molecular tuning of sulfur doped quinoline oligomer derived soft carbon for superior potassium storage[J]. Carbon, 2022, 191: 10-18.
6	JIANG M C, SUN N, ALI SOOMRO R, et al. The recent progress of pitch-based carbon anodes in sodium-ion batteries[J]. Journal of Energy Chemistry, 2021, 55: 34-47.
7	LIU C, ZHENG H J, WANG Y W, et al. Microstructure regulation of pitch-based soft carbon anodes by iodine treatment towards high-performance potassium-ion batteries[J]. Journal of Colloid and Interface Science, 2022, 615: 485-493.
8	LIU C, XIAO N, LI H J, et al. Nitrogen-doped soft carbon frameworks built of well-interconnected nanocapsules enabling a superior potassium-ion batteries anode[J]. Chemical Engineering Journal, 2020, 382: 121759.
9	LIU Q D, HAN F, ZHOU J F, et al. Boosting the potassium-ion storage performance in soft carbon anodes by the synergistic effect of optimized molten salt medium and N/S dual-doping[J]. ACS Applied Materials & Interfaces, 2020, 12(18): 20838-20848.
10	肖南, 邱介山. 煤沥青基功能碳材料的研究现状及前景[J]. 化工进展, 2016, 35(6): 1804-1811.
	XIAO N, QIU J S. Progress in synthesis and applications of functional carbon materials from coal tar pitch[J]. Chemical Industry and Engineering Progress, 2016, 35(6): 1804-1811.
11	WANG Y W, XIAO N, WANG Z Y, et al. Rational design of high-performance sodium-ion battery anode by molecular engineering of coal tar pitch[J]. Chemical Engineering Journal, 2018, 342: 52-60.
12	LIU Y, LU Y X, XU Y S, et al. Pitch-derived soft carbon as stable anode material for potassium ion batteries[J]. Advanced Materials (Deerfield Beach, Fla), 2020, 32(17): e2000505.
13	SUN Q, LI D P, CHENG J, et al. Nitrogen-doped carbon derived from pre-oxidized pitch for surface dominated potassium-ion storage[J]. Carbon, 2019, 155: 601-610.
14	ZHANG G L, GUAN T T, CHENG M, et al. Harvesting honeycomb-like carbon nanosheets with tunable mesopores from mild-modified coal tar pitch for high-performance flexible all-solid-state supercapacitors[J]. Journal of Power Sources, 2020, 448: 227446.
15	ZHUANG Q Q, CAO J P, WU Y, et al. Direct synthesis of oxygen-enriched 3D porous carbons via NaCl template derived from oxidized coal tar pitch for excellent cycling stability electric double layer capacitor[J]. Journal of Power Sources, 2021, 508: 230330.
16	WU J C, WANG J L, GUAN T T, et al. Tailored C-N bond toward defect-rich hierarchically porous carbon from coal tar pitch for high-efficiency adsorptive desulfurization[J]. Fuel, 2021, 292: 120251.
17	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.
18	LIU C, ZHENG H J, YU K, et al. Direct synthesis of P/O-enriched pitch-based carbon microspheres from a coordinated emulsification and pre-oxidation towards high-rate potassium-ion batteries[J]. Carbon, 2022, 194: 176-184.
19	YUAN M, CAO B, MENG C Y, et al. Preparation of pitch-based carbon microbeads by a simultaneous spheroidization and stabilization process for lithium-ion batteries[J]. Chemical Engineering Journal, 2020, 400: 125948.
20	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.
21	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.
22	YUAN F, SHI C H, LI Q L, et al. Unraveling the effect of intrinsic carbon defects on potassium storage performance[J]. Advanced Functional Materials, 2022, 32(48): 2208966.
23	YAO X H, KE Y J, REN W H, et al. Defect-rich soft carbon porous nanosheets for fast and high-capacity sodium-ion storage[J]. Advanced Energy Materials, 2019, 9(6): 1803260.
24	TAN W, WANG L N, LIU K, et al. Bitumen-derived onion-like soft carbon as high-performance potassium-ion battery anode[J]. Small, 2022, 18(39): e2203494.
25	LIU Z Y, WU S J, SONG Y, et al. Non-negligible influence of oxygen in hard carbon as an anode material for potassium-ion batteries[J]. ACS Applied Materials & Interfaces, 2022, 14(42): 47674-47684.
26	YUAN F, ZHANG D, LI Z J, et al. Unraveling the intercorrelation between micro/mesopores and K migration behavior in hard carbon[J]. Small, 2022, 18(12): e2107113.
27	AUGUSTYN V, COME J, LOWE M A, et al. High-rate electrochemical energy storage through Li⁺ intercalation pseudocapacitance[J]. Nature Materials, 2013, 12(6): 518-522.
28	LI D P, CHEN L, CHEN L N, et al. Potassium gluconate-derived N/S Co-doped carbon nanosheets as superior electrode materials for supercapacitors and sodium-ion batteries[J]. Journal of Power Sources, 2019, 414: 308-316.

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乳化/氧化协同制备高倍率钾离子电池负极用沥青基碳微球

Coordinated preparation of pitch-based carbon microspheres for anode materials of high-rate potassium-ion batteries by emulsification/oxidation

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