MOFs及其衍生物作为锂离子电池电极的研究进展

doi:10.12028/j.issn.2095-4239.2019.0159

摘要/Abstract

摘要：

锂离子电池是一种新型的二次能源，担负着未来电池发展的新方向，广泛应用于人们的生产生活中，但商品化锂离子电池的能量密度和循环性能目前还难以满足生产力发展的需求。人们在探寻性能更优的锂离子电池电极材料时，发现具有多孔以及大比表面积特性的金属有机骨架材料(MOFs)及其相应的衍生物相比传统电极材料，在提高锂离子扩散速率、缓解体积变化和保证循环稳定性方面具备更好的优势，因此，MOFs及其衍生物是一种非常有潜力的锂离子电池电极材料。为此，本文主要通过对近期相关文献的探讨，对MIL、MOF、ZIF和普鲁士蓝系列MOFs及其衍生物作为锂电池负极和正极的研究进行详细综述，着重介绍了上述材料的制备方法以及锂离子电池容量提高的影响机理，得出MOFs及其衍生物较好的电荷负载能力和多孔结构的特点，是相对于传统锂离子电池电极性能更优的原因。最后指出针对目前MOFs类电极材料遇到的最大问题，未来应在与其他导电材料复合，机械化学合成方法和不依赖昂贵材料三个发展方向进行努力，有望实现MOFs类锂离子电池电极材料的商业化发展。

关键词: 锂离子电池, 金属有机骨架材料, MOFs衍生物, 负极材料, 正极材料

Abstract:

The lithium-ion battery is a new type of secondary energy storage device, representing a new direction of future battery development, and is extensively used in production and daily life. However, the energy density and cycling performance of the commercial lithium-ion batteries remain insufficient to satisfy the demands of productivity development. On seeking better-performing electrode materials for lithium-ion batteries, metal–organic framework materials (MOFs) with their porous structures and high specific surface areas as well as their corresponding derivatives exhibit advantages over traditional electrode materials because of their improved lithium-ion diffusion rate, reduced volume changes, and increased cycling stability, which make them highly promising lithium-ion battery electrode materials. Therefore, this study mainly reviews the MIL, MOF, ZIF, and Prussian blue series MOFs and their derivatives as negative and positive electrodes of lithium batteries based on the discussion of recent related literature. The preparation methods of the above materials and the mechanism of capacity improvement of the lithium-ion batteries are also emphasized. The influence mechanism of the increase in the lithium-ion battery capacity shows that the charge loading capacity and porous structures of MOFs and their derivatives make them superior to conventional lithium-ion battery materials. Finally, based on the most significant issues currently associated with the MOF electrode materials, future research should focus on three development directions, i.e., composites with other conductive materials, mechanochemical syntheses, and the use of inexpensive materials, to realize the commercial development of MOF electrode materials for lithium-ion batteries.

Key words: lithium ion battery, metal organic framework materials, MOFs derivatives, anode materials, cathode materials

中图分类号:

TM 912

李震东, 王振华, 张仕龙, 符春林. MOFs及其衍生物作为锂离子电池电极的研究进展[J]. 储能科学与技术, 2020, 9(1): 18-24.

LI Zhendong, WANG Zhenhua, ZHANG Shilong, FU Chunlin. Research progress of MOFs and its derivatives as electrode materials for lithium ion batteries[J]. Energy Storage Science and Technology, 2020, 9(1): 18-24.

图/表 7

图1

图2

图3

图4

图5

图6

图7

参考文献 33

1	EDDAOUDI M , KIM J , ROSI N L , et al . Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage[J]. Science, 2002, 295(5554): 469-472.
2	RAGON F , CAMPO B , YANG Q , et al . Acid-functionalized UIO-66(Zr) MOFs and their evolution after intra-framework cross-linking: Structural features and sorption properties[J]. Journal of Materials Chemistry, 2015, 3(7): 3294-3309.
3	WANG W , YUAN Y , SUN F X , et al . Targeted synthesis of novel porous aromatic frameworks with selective separation of CO₂/CH₄ and CO₂/N₂ [J]. Chinese Chemical Letters, 2014, 25(11): 1407-1410.
4	ZHANG T , LIN W B . Metal-organic frameworks for artificial photosynthesis and photocatalysis[J]. Chemical Society Reviews, 2014, 43(16): 5982-5993.
5	WANG L , HAN Y Z , FENG X , et al . Metal-organic frameworks for energy storage: Batteries and supercapacitors[J]. Coordination Chemistry Reviews, 2016, 307: 361-381.
6	LI G H , YANG H , LI F C , et al . Facile formation of a nanostructured NiP2@C material for advanced lithium-ion battery anode using adsorption property of metal-organic framework[J]. Journal of Materials Chemistry, 2016, 4(24): 9593-9599.
7	FEREY G , MELLOTDRAZNIEKS C , SERRE C , et al . A chromium terephthalate-based solid with unusually large pore volumes and surface area[J]. Science, 2005, 309(5743): 2040-2042.
8	FEREY G , LATROCHE M , SERRE C , et al . Hydrogen adsorption in the nanoporous metal-benzenedicarboxylate M(OH)(O₂C–C₆H₄–CO₂)(M=Al³⁺, Cr³⁺), MIL-53[J]. Chemical Communications, 2003, 24: 2976-2977.
9	LI G H , LI F C , YANG H Y , et al . Graphene oxides doped MIL-101(Cr) as anode materials for enhanced electrochemistry performance of lithium ion battery[J]. Inorganic Chemistry Communications, 2016, 64: 63-66.
10	赵思维, 孙雪梅, 孙宇涵, 等 . 基于金属有机骨架材料为前驱物的锂电负极材料α-Fe₂O₃的合成及性能表征[J]. 科学技术与工程, 2016, 16(30): 1-5.
	ZHAO Siwei , SUN Xuemei , SUN Yuhan , et al . Synthesis and electrochemical performance of α-Fe₂O₃ anode material based on MOF as precursor[J]. Science Technology and Engineering, 2016, 16(30): 1-5.
11	LI M C , WANG W X , YANG M Y , et al . Large-scale fabrication of porous carbon-decorated iron oxide microcuboids from Fe-MOF as high-performance anode materials for lithium-ion batteries[J]. RSC Advances, 2015, 5(10): 7356-7362.
12	HUANG G , ZHANG F F , ZHANG L L , et al . Hierarchical NiFe₂O₄/Fe₂O₃ nanotubes derived from metal organic frameworks for superior lithium ion battery anodes[J]. Journal of Materials Chemistry, 2014, 2(21): 8048-8053.
13	LUO Y M , SUN L X , XU F , et al . Porous carbon derived from metal-organic framework as an anode for lithium-ion batteries with improved performance[J]. Key Engineering Materials, 2017, 727: 705-711.
14	LI C , CHEN T Q , XU W J , et al . Mesoporous nanostructured Co₃O₄ derived from MOF template: A high-performance anode material for lithium-ion batteries[J]. Journal of Materials Chemistry, 2015, 3(10): 5585-5591.
15	BAI Z C , ZHANG Y H , ZHANG Y W , et al . MOFs-derived porous Mn₂O₃ as high-performance anode material for Li-ion battery[J]. Journal of Materials Chemistry, 2015, 3(10): 5266-5269.
16	QIU Y C , XU G L , YAN K Y , et al . Morphology-conserved transformation: Synthesis of hierarchical mesoporous nanostructures of Mn₂O₃ and the nanostructural effects on Li-ion insertion/deinsertion properties[J]. Journal of Materials Chemistry, 2011, 21(17): 6346-6353.
17	ZHANG X , QIAN Y T , ZHU Y C , et al . Synthesis of Mn₂O₃ nanomaterials with controllable porosity and thickness for enhanced lithium-ion batteries performance[J]. Nanoscale, 2014, 6(3): 1725-1731.
18	DENG Y F , LI Z , SHI Z N , et al . Porous Mn₂O₃ microsphere as a superior anode material for lithium ion batteries[J]. RSC Advances, 2012, 2(11): 4645-4647.
19	QU Q T , GAO T , ZHENG H Y , et al . Graphene oxides-guided growth of ultrafine Co₃O₄ nanocrystallites from MOFs as high-performance anode of Li-ion batteries[J]. Carbon, 2015, 92: 119-125.
20	LIU J , WU C , XIAO D D , et al . MOF-derived hollow Co₉S₈ nanoparticles embedded in graphitic carbon nanocages with superior Li-ion storage[J]. Small, 2016, 12(17): 2354-2364.
21	WANG Q F , ZOU R Q , XIA W , et al . Facile synthesis of ultrasmall CoS₂ nanoparticles within thin N-doped porous carbon shell for high performance lithium-ion batteries[J]. Small, 2015, 11(21): 2511-2517.
22	YANG D H , ZHOU X L , ZHONG M , et al . A robust hybrid of SnO₂ nanoparticles sheathed by N-doped carbon derived from ZIF-8 as anodes for Li ion batteries[J]. Chemnanomat, 2017, 3: doi: 10.1002/cnma. 201600371.
23	ZHANG L , WU H B , MADHAVI S , et al . Formation of Fe₂O₃ microboxes with hierarchical shell structures from metal-organic frameworks and their lithium storage properties[J]. Journal of the American Chemical Society, 2012, 134(42): 17388-17391.
24	YANG X , TANG Y B , HUANG X , et al . Lithium ion battery application of porous composite oxide microcubes prepared via metal-organic frameworks[J]. Journal of Power Sources, 2015, 284: 109-114.
25	LUO J S , XIA X H , LUO Y S , et al . Rationally designed hierarchical TiO₂@Fe₂O₃ hollow nanostructures for improved lithium ion storage[J]. Advanced Energy Materials, 2013, 3(6): 737-743.
26	LI Z Q , LI B , YIN L W , et al . Prussion blue-supported annealing chemical reaction route synthesized double-shelled Fe₂O₃/Co₃O₄ hollow microcubes as anode materials for lithium-ion battery[J]. ACS Applied Materials & Interfaces, 2014, 6: doi: 10.1021/am500417j.
27	ABBAS S M , HUSSAIN S T , ALI S, et al . Modification of carbon nanotubes by CuO-doped NiO nanocomposite for use as an anode material for lithium-ion batteries[J]. Journal of Solid State Chemistry, 2013, 202: 43-50.
28	ZHENG F C , ZHU D Q , CHEN Q W , et al . MOF-derived self-assembled ZnO/Co₃O₄nanocomposite clusters as high-performance anodes for lithium-ion batteries[J]. Dalton Transactions, 2015, 44(38): doi： 10.1039/c5dt02271a.
29	HUANG G , ZHANG L L , ZHANG F F , et al . Metal-organic framework derived Fe₂O₃@NiCo₂O₄ porous nanocages as anode materials for Li-ion batteries[J]. Nanoscale, 2014, 6(10): 5509-5515.
30	HAMEED A S , REDDY M V , CHOWDARI B V , et al . Carbon coated Li₃V₂(PO₄)₃ from the single-source precursor, Li₂(VO)₂(HPO₄)₂(C₂O₄)·6H₂O as cathode and anode materials for lithium ion batteries[J]. Electrochimica Acta, 2014, 128: 184-191.
31	ZHANG Z Y , YOSHIKAWA H , AWAGA K , et al . Monitoring the solid-state electrochemistry of Cu(2, 7-AQDC) (AQDC=anthraquinone dicarboxylate) in a lithium battery: Coexistence of metal and ligand redox activities in a metal-organic framework[J]. Journal of the American Chemical Society, 2014, 136(46): 16112-16115.
32	SHIN J , KIM M , CIRERA J , et al . MIL-101(Fe) as a lithium-ion battery electrode material: A relaxation and intercalation mechanism during lithium insertion[J]. Journal of Materials Chemistry, 2015, 3(8): 4738-4744.
33	SHEN L , WANG Z X , CHEN L Q , et al . Prussian blues as a cathode material for lithium ion batteries[J]. Chemistry: A European Journal, 2014, 20(39): 12559-12562.

[1]	李海涛, 孔令丽, 张欣, 余传军, 王纪威, 徐琳. N/P设计对高镍NCM/Gr电芯性能的影响[J]. 储能科学与技术, 2022, 11(7): 2040-2045.
[2]	陈龙, 夏权, 任羿, 曹高萍, 邱景义, 张浩. 多物理场耦合下锂离子电池组可靠性研究现状与展望[J]. 储能科学与技术, 2022, 11(7): 2316-2323.
[3]	易顺民, 谢林柏, 彭力. 基于VF-DW-DFN的锂离子电池剩余寿命预测[J]. 储能科学与技术, 2022, 11(7): 2305-2315.
[4]	祝庆伟, 俞小莉, 吴启超, 徐一丹, 陈芬放, 黄瑞. 高能量密度锂离子电池老化半经验模型[J]. 储能科学与技术, 2022, 11(7): 2324-2331.
[5]	刘显茜, 孙安梁, 田川. 基于仿生翅脉流道冷板的锂离子电池组液冷散热[J]. 储能科学与技术, 2022, 11(7): 2266-2273.
[6]	徐雄文, 聂阳, 涂健, 许峥, 谢健, 赵新兵. 普鲁士蓝正极软包钠离子电池的滥用性能[J]. 储能科学与技术, 2022, 11(7): 2030-2039.
[7]	王宇作, 王瑨, 卢颖莉, 阮殿波. 孔结构对软碳负极储锂性能的影响[J]. 储能科学与技术, 2022, 11(7): 2023-2029.
[8]	孔为, 金劲涛, 陆西坡, 孙洋. 对称蛇形流道锂离子电池冷却性能[J]. 储能科学与技术, 2022, 11(7): 2258-2265.
[9]	霍思达, 薛文东, 李新丽, 李勇. 基于CiteSpace知识图谱的锂电池复合电解质可视化分析[J]. 储能科学与技术, 2022, 11(7): 2103-2113.
[10]	邓健想, 赵金良, 黄成德. 高能量锂离子电池硅基负极黏结剂研究进展[J]. 储能科学与技术, 2022, 11(7): 2092-2102.
[11]	申晓宇, 岑官骏, 乔荣涵, 朱璟, 季洪祥, 田孟羽, 金周, 闫勇, 武怿达, 詹元杰, 俞海龙, 贲留斌, 刘燕燕, 黄学杰. 锂电池百篇论文点评（2022.4.1—2022.5.31）[J]. 储能科学与技术, 2022, 11(7): 2007-2022.
[12]	周伟, 符冬菊, 刘伟峰, 陈建军, 胡照, 曾燮榕. 废旧磷酸铁锂动力电池回收利用研究进展[J]. 储能科学与技术, 2022, 11(6): 1854-1864.
[13]	张浩然, 车海英, 郭凯强, 申展, 张云龙, 陈航达, 周煌, 廖建平, 刘海梅, 马紫峰. Sn掺杂NaNi_1/3Fe_1/3Mn_1/3-_x Sn _x O₂ 正极材料制备及其电化学性能[J]. 储能科学与技术, 2022, 11(6): 1874-1882.
[14]	张言, 王海, 刘朝孟, 张德柳, 王佳东, 李建中, 高宣雯, 骆文彬. 锂离子电池富镍三元正极材料NCM的研究进展[J]. 储能科学与技术, 2022, 11(6): 1693-1705.
[15]	丁奕, 杨艳, 陈锴, 曾涛, 黄云辉. 锂离子电池智能消防及其研究方法[J]. 储能科学与技术, 2022, 11(6): 1822-1833.