一步水热法制备三维石墨烯/Fe3O4 复合材料及其储锂性能

doi:10.19799/j.cnki.2095-4239.2022.0761

摘要/Abstract

摘要：

Fe₃O₄作为锂离子电池负极材料，在充放电时体积变化较大，导致其容量衰减严重。目前，碳包覆是解决这个问题的主要方式之一。本工作以氧化石墨烯(GO)和Fe²⁺为原料，用一步水热法合成了三维石墨烯片包覆Fe₃O₄纳米颗粒3DG@Fe₃O₄复合材料。使用傅里叶红外光谱(FT-IR)仪、热重分析(TGA)仪、X射线衍射(XRD)仪、拉曼光谱(Raman)仪、扫描电子显微镜(SEM)对复合物进行表征，研究结果表明，复合材料呈现石墨烯(G)片包覆Fe₃O₄纳米颗粒的三明治结构。同时采用了恒流充放电(GCPL)、循环伏安(CV)以及交流阻抗(EIS)等电化学测试方法，着重研究了Fe₃O₄含量对其电化学性能的影响，Fe₃O₄质量分数为83.2%的3DG@Fe₃O₄-2电极具有最高的比容量和循环性能，在0.1 A/g的电流密度下的首次放电比容量为1412.33 mAh/g，循环100次后的放电比容量为577 mAh/g，是纯Fe₃O₄电极材料经历100次循环后的6.5倍。一步水热合成方法具有操作简单、合成条件温和及无需额外添加还原剂等优点；制备的复合电极相比纯Fe₃O₄具有电极容量高、循环稳定性能好的优势，有助于推动Fe₃O₄基负极材料在电化学领域中的应用。

关键词: 水热法, 碳包覆, 四氧化三铁(Fe₃O₄), 锂离子电池, 负极材料

Abstract:

As a lithium-ion battery anode material, the Fe₃O₄exhibits varying volume during charging and discharging, which results in serious capacity degradation. This problem can be solved using carbon coating. Thus, in this paper, three-dimensional graphene-coated Fe₃O₄ nanoparticle(3DG@Fe₃O₄) composites were synthesized by one-step hydrothermal method using graphene oxide (GO) and Fe²⁺as raw materials. The composites were characterized by a Fourier transform infrared spectrometer, thermal gravimetric analyzer, X-ray diffractometer, Raman spectrometer and scanning electron microscopy. The results showed that the composites have a "sandwich" structure of graphene (G)-coated Fe₃O₄ nanoparticles. Meanwhile, electrochemical tests, including galvanostatic cycling with potential limitation, cyclic voltammetry, and alternating current impedance were used to investigate the influence of Fe₃O₄content on the lithium-ion storage performance of 3DG@Fe₃O₄ composites. The 3DG@Fe₃O $4$ -2 electrode with about 83.2% Fe₃O₄ exhibited enhanced specific capacity and better cycle stability. It also delivered a high discharge specific capacity of 1412.33 mAh/g at a current density of 0.1 A/g and 577 mAh/g after 100 cycles, and this value was 6.5 times that of pure Fe₃O₄ electrode material after 100 cycles. The composites prepared by this method have simple synthesis and do not require additional reducing agent. The prepared composites have high capacity and good cycle stability compared with pure Fe₃O₄ nanoparticles, and this can promote the application of Fe₃O₄-based anode materials in the field of energy storage.

Key words: hydrothermal process, carbon coating, Fe₃O₄, lithium-ion battery, anode material

中图分类号:

TQ 152

成雪莉, 张维福, 罗城城, 袁小亚. 一步水热法制备三维石墨烯/Fe₃O₄ 复合材料及其储锂性能[J]. 储能科学与技术, 2023, 12(4): 1066-1074.

Xueli CHENG, Weifu ZHANG, Chengcheng LUO, Xiaoya YUAN. Preparation of three-dimensional graphene/Fe₃O₄composites by one-step hydrothermal method and their lithium storage performance[J]. Energy Storage Science and Technology, 2023, 12(4): 1066-1074.

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参考文献 24

1	MOSALLANEJAD B, MALEK S S, ERSHADI M, et al. Cycling degradation and safety issues in sodium-ion batteries: Promises of electrolyte additives[J]. Journal of Electroanalytical Chemistry, 2021, 895: doi: 10.1016/j.jelechem.2021.115505.
2	YANG M, ZHANG W, SU D, et al. Flexible SnTe/carbon nanofiber membrane as a free-standing anode for high-performance lithium-ion and sodium-ion batteries[J]. Journal of Colloid and Interface Science, 2022, 605: 231-240.
3	XUE H, FANG Y X, ZENG L X, et al. Facile synthesis of hierarchical lychee-like Zn₃V₃O₈@C/rGO nanospheres as high-performance anodes for lithium ion batteries[J]. Journal of Colloid and Interface Science, 2019, 533: 627-635.
4	LI J, HWANG S, GUO F M, et al. Phase evolution of conversion-type electrode for lithium ion batteries[J]. Nature Communications, 2019, 10(1): 1-10.
5	PHAM-CONG D, KIM S J, JEONG S Y, et al. Enhanced cycle stability of iron(II, III) oxide nanoparticles encapsulated with nitrogen-doped carbon and graphene frameworks for lithium battery anodes[J]. Carbon, 2018, 129: 621-630.
6	WEI W, YANG S B, ZHOU H X, et al. 3D graphene foams cross-linked with pre-encapsulated Fe₃O₄ nanospheres for enhanced lithium storage[J]. Advanced Materials (Deerfield Beach, Fla), 2013, 25(21): 2909-2914.
7	YU S H, LEE S H, LEE D J, et al. Conversion reaction-based oxide nanomaterials for lithium ion battery anodes[J]. Small (Weinheim an Der Bergstrasse, Germany), 2016, 12(16): 2146-2172.
8	JUNG S K, HWANG I, CHANG D, et al. Nanoscale phenomena in lithium-ion batteries[J]. Chemical Reviews, 2020, 120(14): 6684-6737.
9	ERSHADI M, JAVANBAKHT M, BRANDELL D, et al. Facile synthesis of amino-functionalized mesoporous Fe₃O₄/rGO 3D nanocomposite by diamine compounds as Li-ion battery anodes[J]. Applied Surface Science, 2022, 601: doi: 10.1016/j.apsusc.2022.154120.
10	ZHANG L, WU HAO BIN, LOU X W D. Iron-oxide-based advanced anode materials for lithium-ion batteries[J]. Advanced Energy Materials, 2014, 4(4): doi: 10.1002/aenm.201300958.
11	WU Q C, JIANG R L, LIU H W. Carbon layer encapsulated Fe₃O₄@Reduced graphene oxide lithium battery anodes with long cycle performance[J]. Ceramics International, 2020, 46(8): 12732-12739.
12	LIU G, SHAO J, GAO Y J, et al. Green fabrication of sandwich-like and dodecahedral C@Fe₃O₄@C as high-performance anode for lithium-ion batteries[J]. Journal of Solid State Electrochemistry, 2017, 21(9): 2593-2600.
13	CONG H P, REN X C, WANG P, et al. Macroscopic multifunctional graphene-based hydrogels and aerogels by a metal ion induced self-assembly process[J]. ACS Nano, 2012, 6(3): 2693-2703.
14	赵婷婷, 李小强, 张亚梅, 等. CoFe₂O₄@C复合纳米纤维膜作为自支撑锂离子电池负极[J]. 复合材料学报, 2022, 39(9): 4431-4440.
	ZHAO T T, LI X Q, ZHANG Y M, et al. CoFe₂O₄@C composite nanofiber films as self-standing anodes for lithium-ion batteries[J]. Acta Materiae Compositae Sinica, 2022, 39(9): 4431-4440.
15	JIANG X, MA Y W, LI J J, et al. Self-assembly of reduced graphene oxide into three-dimensional architecture by divalent ion linkage[J]. The Journal of Physical Chemistry C, 2010, 114(51): 22462-22465.
16	ZHANG M, JIA M Q. High rate capability and long cycle stability Fe₃O₄-graphene nanocomposite as anode material for lithium ion batteries[J]. Journal of Alloys and Compounds, 2013, 551: 53-60.
17	吴启超. Fe₃O₄@rGO/C锂离子电池负极材料制备与性能研究[D]. 徐州: 中国矿业大学, 2020.
	WU Q C. Study on the preparation and performance of Fe₃O₄@rGO/C anode materials for lithium ion batteries[D]. Xuzhou: China University of Mining and Technology, 2020.
18	夏东, 黄朋, 李恒. 水热法制备三维导电石墨烯气凝胶及其焦耳热性能研究[J]. 化工学报, 2021, 72(7): 3839-3848.
	XIA D, HUANG P, LI H. Joule-heating studies of electrically conducting three-dimensional graphene aerogels prepared by hydrothermal assembly[J]. CIESC Journal, 2021, 72(7): 3839-3848.
19	李晨, 熊传溪. Fe₃O₄/纳米纤维素气凝胶负极材料的制备及电化学性能[J]. 储能科学与技术, 2018, 7(3): 512-518.
	LI C, XIONG C X. The preparation of Fe₃O₄/nanocellulose aerogel nanocomposite as anodes for lithium-ion batteries and electrochemical performance[J]. Energy Storage Science and Technology, 2018, 7(3): 512-518.
20	WANG N, LIU Q L, LI Y, et al. Self-crosslink assisted synthesis of 3D porous branch-like Fe₃O₄/C hybrids for high-performance lithium/sodium-ion batteries[J]. RSC Advances, 2017, 7(79): 50307-50316.
21	ZHANG Y G, LI Y, LI H P, et al. Electrochemical performance of carbon-encapsulated Fe₃O₄ nanoparticles in lithium-ion batteries: Morphology and particle size effects[J]. Electrochimica Acta, 2016, 216: 475-483.
22	AURBACH D, LEVI M D, LEVI E, et al. Common electroanalytical behavior of Li intercalation processes into graphite and transition metal oxides[J]. Journal of the Electrochemical Society, 1998, 145(9): 3024-3034.
23	SHI Y, ZHANG J, BRUCK A M, et al. Conductive polymers: A tunable 3D nanostructured conductive gel framework electrode for high-performance lithium ion batteries[J]. Advanced Materials, 2017, 29(22): doi: 10.1002/adma.201603922.
24	杨志伟. 铁基氧化物/石墨烯纳米复合材料的制备及其储锂性能研究[D]. 天津: 天津大学, 2017.
	YANG Z W. Synthesis and lithium-storage performance of Fe-based oxides/graphene nanocomposites[D]. Tianjin: Tianjin University, 2017.

样品	R_f/Ω	R_ct/Ω
Fe₃O₄	83.6	567.5
3DG@Fe₃O₄-1	16.2	389.4
3DG@Fe₃O₄-2	11.4	316.9
3DG@Fe₃O₄-2(50th)	6.6	126.7
3DG@Fe₃O₄-3	14.5	350.1

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一步水热法制备三维石墨烯/Fe₃O₄ 复合材料及其储锂性能

Preparation of three-dimensional graphene/Fe₃O₄composites by one-step hydrothermal method and their lithium storage performance

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