Corresponding Author

Ming-sen ZHENG(mszheng@xmu.edu.cn);
Quan-feng DONG(qfdong@xmu.edu.cn)


Metal–organic framework(MOF) is a kind of novel electrode materials for lithium ion batteries. Here, a composite material Co3(HCOO)6@rGO was synthesized for the first time by in situ loading of Co3(HCOO)6 on rGO (reduced oxide graphene) through a solution chemistry method. As an anode material for lithium ion batteries, it exhibited an excellent cycle stability as well as a large reversible capacity of 926 mAh·g-1 at a current density of 500 mA·g-1 after 100 cycles within the voltage range of 0.02 ~ 3.0 V vs. Li/Li+ with a good rate capability. The results of cyclic voltammetry and XPS measurements revealed that both Co2+ and formate ions in Co3(HCOO)6@rGO uderwent reversible electrochemical reactions during the charge and discharge process. Compared with Co3(HCOO)6 synthesized through the same method, it was found that rGO could activate the electrochemical reaction of formate ion, which improved the Co3(HCOO)6 rate performance.A new route was demonstrated through this work to enhance the specific capacity and rate capability of MOFs by introducing rGO.

Graphical Abstract


Co3(HCOO)6@rGO; Co3(HCOO)6, formate ion, anode, lithium ion batteries

Publication Date


Online Available Date


Revised Date


Received Date



[1] Armand M, Tarascon J M. Building better batteries[J]. Naure, 2008, 451(7179): 652-657.
[2] Chu D B(褚道葆), Li J(李建), Yuan X M(袁希梅), et al. Tin-based alloy anode materials for lithium ion batteries[J]. Progress in Chemistry(化学进展), 2012, 27(8): 1466-1476.
[3] Huang X L, Wang R Z, Xu D, et al. Homogeneous CoO on graphene for binder-free and ultralong-life lithium ion batteries[J]. Advanced Functional Materials, 2013, 23(35): 4345-4353.
[4] Armand M, Grugeon S, Vezin H, et al. Conjugated dicarboxylate anodes for Li-ion batteries[J]. Nature Materials, 2009, 8(2): 120-125.
[5] Wang S, Wang L, Zhang K, et al. Organic Li4C8H2O6 nano-sheets for lithium-ion batteries[J]. Nano Letters, 2013, 13(9): 4404-4409.
[6] Long J R, Yaghi O M. The pervasive chemistry of metal-organic frameworks[J]. Chemical Society Reviews, 2009, 38(5): 1213-1214.
[7] Ke F S, Wu Y S, Deng H. Metal-organic frameworks for lithium ion batteries and supercapacitors[J]. Journal of Solid State Chemistry, 2015, 223(S1): 109-121.
[8] Liu Y, Wang Z U, Zhou H C. Recent advances in carbon dioxide capture with metal-organic frameworks[J]. Greenhouse Gases: Science and Technology, 2012, 2(4): 239-259.
[9] Wang Z, Chen G, Ding K. Self-supported catalysts[J]. Chemical Reviews, 2009, 109(2): 322-359.
[10] Vallet-Regí M, Balas F, Arcos D. Mesoporous materials for drug delivery[J]. Angewandte Chemie International Edition, 2007, 46(40): 7548-7558.
[11] Motokawa N, Matsunaga S, Takaishi S, et al. Reversible magnetism between an antiferromagnet and a ferromagnet related to solvation/desolvation in a robust layered [Ru2]2TCNQ charge-transfer system[J]. Journal of the American Chemical Society, 2010, 132(34): 11943-11951.
[12] Liu K, You H P, Zheng Y H, et al. Facile and rapid fabrication of metal-organic framework nanobelts and colortunable photoluminescence properties[J]. Journal of Materials Chemistry, 2010, 20(16): 3272-3279.
[13] Li X, Cheng F, Zhang S, et al. Shape-controlled synthesis and lithium-storage study of metal-organic frameworks Zn4O(1,3,5-benzenetribenzoate)2[J]. Journal of Power Sources, 2006, 160(1): 542-547.
[14] Gou L, Hao L M, Shi Y X, et al. One-pot synthesis of a metal-organic framework as an anode for Li-ion batteries with improved capacity and cycling stability[J]. Journal of Solid State Chemistry, 2014, 210(1): 121-124.
[15] Su F Y, You C, He Y B, et al. Flexible and planar graphene conductive additives for lithium-ion batteries[J]. Journal of Materials Chemistry, 2010, 20(43): 9644-9650.
[16] Wang Z, Zhang B, Kurmoo M, et al. Synthesis and characterization of a porous magnetic diamond framework, Co3(HCOO)6, and its N2 sorption characteristic[J]. Inorganic Chemistry, 2005, 44(5): 1230-1237.
[17] Guo J C, Liu Q, Wang C S, et al. Interdispersed amorphous mnox-carbon nanocomposites with superior electrochemical performance as lithium-storage material[J]. Advanced Functional Materials, 2012, 22(4): 803-811.
[18] Wang L P, Mou C X, Sun Y, et al. Structure-property of metal organic frameworks calcium terephthalates anodes for lithium-ion batteries[J]. Electrochimica Acta, 2015, 173: 235-241.
[19] Khassin A A, Yurieva T M, Kaichev V V, et al. Metal-support interactions in cobalt-aluminum co-precipitated catalysts: XPS and CO adsorption studies[J]. Journal of Molecular Catalysis A: Chemical, 2001, 175(1/2): 189-204.
[20] Kocijan A, Milošev I, Pihlar B. Cobalt-based alloys for orthopaedic applications studied by electrochemical and XPS analysis[J]. Journal of Materials Science: Materials in Medicine, 2004, 15(6): 643-650.
[21] Fu L, Liu Z M, Liu Y Q, et al. Beaded cobalt oxide nanoparticles along carbon nanotubes: Towards more highly integrated electronic devices[J]. Advanced Materials, 2005, 17(2): 217-221.
[22] Coulter K E, Sault A G. Effects of activation on the surface properties of silica-supported cobalt catalysts[J]. Journal of Catalysis, 1995, 154(1): 56-64.
[23] Yang Z, Xu X, Liang X, et al. MIL-53(Fe)-graphene nanocomposites: Efficient visible-light photocatalysts for the selective oxidation of alcohols[J]. Applied Catalysis B: Environmental, 2016, 198: 112-123.
[24] Sivaprakash S, Majumder S B. Spectroscopic analyses of 0.5Li[Ni0.8Co0.15Zr0.05]O2-0.5Li[Li1/3Mn2/3]O2 composite cathodes for lithium rechargeable batteries[J]. Solid State Ionics, 2010, 181(15/16): 730-739.
[25] Leroy S, Martinez H, Dedryvère R, et al. Influence of the lithium salt nature over the surface film formation on a graphite electrode in Li-ion batteries: An XPS study[J]. Applied Surface Science, 2007, 253(11): 4895-4905.



To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.