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Mangnese 3, 5-pyridinedicarboxylate anode material for Li-ion batteries showed good cycling stability.
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ARTICLE TYPE
Metal dicarboxylates: new anode materials for lithium-ion batteries with good cycling performance Hailong Fei,*a, b Xin Liu, a Zhiwei Lia, Wenjing Feng a 5
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Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX DOI: 10.1039/b000000x A simple and versatile method for preparation of manganese coordination polymer [Mn (3, 5-PDC) •2H2O] (3, 5-H2PDC = 3, 5-pyridinedicarboxylic acid) and Mn 2, 5-furandicarboxylate is developed via a simple hydrothermal route, which are firstly tested as novel high-energy anode materials for lithium-ion batteries. [Mn (3, 5-PDC) •3H2O] shows a high discharge capacity of 583.9 mAhg-1 for the fourth cycle between a 0.05 – 3.0 V voltage limit at a discharge current density of 100 mAg-1. The reversible capacity of 554.0 mAhg-1 is remained after 240 cycles with a capacity retention being 94.8%. While Mn 2, 5furandicarboxylate shows a high discharge capacity of 467.3 mAhg-1 for the second cycle. The reversible capacity of 436.6 mAhg-1 is remained after 206 cycles with a capacity retention being 93.4%.
1. Introduction 15
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Nowadays, there is a remarkable demand for rechargeable batteries with reversible and efficient electrochemical energy storage and conversion in the field of portable electronic consumer devices, electric vehicles, and large-scale electricity storage in smart and intelligent grids as renewable clean energy to lessen energy crisis.1,2 Lithium-ion battery is one of the promising rechargeable batteries for high energy density coupled with long life cycle and rate capability.3 The current concerns are driving an enormous variety of interests aimed at achieving low cost, sustainable and renewable, high safety and energy-density electrode materials for lithium-ion batteries. Bio-inspired and conjugated dicarboxylate Li2C8H4O4 (Li terephthalate) and Li2C6H4O4 (Li trans–trans-muconate) are capable of reacting with two and one extra Li per formula unit at potentials of 0.8 and 1.4 V, giving reversible capacities of 300 and 150 mAhg-1, respectively.4 Recently, other organic dicarboxylates have been widely studied as cathodes for lithium-ion batteries, such as 2, 6naphthalene dicarboxylate dilithium (2, 6-Naph (COOLi) 2), 5, 6 lithium 4, 40-tolane-dicarboxylate7 and metal-1, 4, 5, 8naphthalenetetracarboxylates.8 It is reported that several coordination polymer showed electrochemical activity for lithium-ion batteries. A Li-O bonds bridged coordination polymer Li2C6H2O4 with carbonyl groups and 2-D layered aromatic rings indicate that it can be used as cathode materials for lithium-ion batteries, but bad cycling stability was obtained.9 Manganesebased layered coordination polymer (Mn-(tfbdc)(4,4’-bpy)(H2O)2) with microporous structure was prepared by reaction of 2, 3, 5, 6tetrafluoroterephthalatic acid (H2tfbdc) and 4, 4’- bipyridine (4, 4’ - bpy) with manganese (II) acetate tetrahydrate in water solution, showing a low lithium storage capacity of 390 mAhg-1 for high molecular weight and rigid organic framework.10 polypyrrole-nickel-oxygen (PPy-Ni-O),11 PPy-Fe-O,12 and PPyThis journal is © The Royal Society of Chemistry [year]
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Co-O13 coordination complex were also reported as anode maerials for lithium-ion batteries with high capacity and good cycling performance. Transition metal dicarboxylates offer the advantages of being easy to synthesize, environmental friendly, high thermal stability, sustainable, and renewable characters. However, they have not been attracted many interests in energy conversion and storage, for example, coordination polymers based on 3, 5pyridinedicarboxylic acid. The attention mainly focused on the synthesis and crystal characterizations of Co(3,5pdc)(H2O)•(glycol), Ni(3,5-pdc)(H2O)(glycol)•(H2O) ,14 Mn (3, 5-pdc) • 2H2O15 and metal (Ni, Pb, Co) organic frameworks based on pyridine-3,5-dicarboxylic acid and two chelate ligands .16 Lanthanide (III) - cobalt (II) coordination complexes constructed with deprotonated 3, 5-pyridinedicarboxylic acid ligand,17 and Co-Cu coordination polymer with different content of water 18 were also reported. Herein, we developed a simple way to fabricate manganese, cobalt and zinc based 3, 5-pyridinedicarboxylate as well as manganese furandicarboxylate. When used as anode material for lithium-ion batteries, manganese based coordination polymer showed the highest discharge capacity and best cycling stability than cobalt and zinc based counterpart.
2. Experimental
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All chemicals are commercially available and were used as received. The preparation was performed via a hydrothermal method in an absolute alcohol - water mixed solvent. In a typical procedure, equal mmol 3, 5-pyridinedicarboxylic acid and manganese (II) acetate tetrahydrate was added to the water solution and stirred at room temperature for 2 hours. After that, the mixture was transferred to a 50-ml Teflon-lined stainless autoclave, sealed, kept at certain temperature for 24 hours, cooled to room temperature, washed with absolute alcohol and dried at
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70 OC for 12 hours. When manganese (II) acetate tetrahydrate was taken the place of by equal molar cobalt and zinc nitrates, cobalt and zinc based compounds were synthesized under the identical condition. Maganese furandicarboxylate was prepared with 2, 5-furandicarboxylic acid and manganese (II) acetate tetrahydrate under the similar condition. The morphological characteristics of the as-synthesized materials were observed with a Hitachi S-4800 field emission scanning electron microscope (SEM). X-ray diffraction (XRD) patterns were recorded on a diffractometer (Co Kα, PANalytical, and X’Pert). Thermal analysis measurements were performed using a German Netzsch DIL402C Aanalyzer. The FT-IR spectra were recorded on an America Thermo Fisher Scientific Nicolet 6700 spectrometer. A Land CT2001A battery tester was used to measure the electrode activities at room temperature. The as-synthesized coordination polymers were tested as anode materials for lithium-ion batteries. The composite of negative electrode material was consisted of the active material, a conductive material (super-pure carbon) and binder polyvinylidene difluoride (PVDF) in a weight ratio of 6/3/1. The Li metal was used as the counter electrode. The cells were charged and discharged between a 0.05 - 3.0 V voltage limit.
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molecules between the layers and the hydrogen bonds from water and carboxylic acid groups link the layers to form a three dimensional structure [15]. The corresponding coordination mode was shown in Fig. 2. It can also be seen that zinc and cobalt 3, 5pyridinedicarboxylates have similar diffraction peaks to Mn (3, 5PDC) •2H2O after 37o in Fig. 1b, and c, respectively, implying that they might have similar composition. But the diffraction peaks are very different to each other before 37o, which may be due to the different coordination essence of Mn2+, Zn2+ and Co2+ with 3, 5-pyridinedicarboxylic acid.
Fig. 2 Coordination mode of 3, 5-pyridinedicarboxylic acid.
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Fig. 1 Wide-angle powder XRD patterns of the as-synthesized coordination polymers based on different metal a) Mn, b) Zn, c) Co and d) the wide angle XRD patterns obtained from single crystal Mn (3, 5-PDC) •2H2O. Manganese 3, 5-pyridinedicarboxylic acid coordination polymer was prepared via a facile solvo-thermal method, as described in the experimental section. X-ray diffraction was performed to identify the crystalline structure in Fig. 1. The diffraction peaks are centered at 15.06, 18.4, 19.06, 23.73, 28.12, 29.07, 29.93, 34.69, 35.45, 37.36, 38.03, 38.79, 39.36, 40.12, 40.79, 41.74, 42.31, 44.51, 45.65, 46.41, 48.03, 49.56, 50.51, 51.27, 52.89, 53.46, 54.52, 56.51, 58.52 and 59.28 in Fig. 1a. It can be ascribed to the reported coordination polymer Mn (3, 5PDC) •2H2O (H2PDC= 3, 5-pyridinedicarboxylic acid) via comparing the wide angle XRD patterns of single crystal Mn (3, 5-PDC) •2H2O from ours, in which each 3,5-pdc ligand bridges three Mn (Ⅱ) centers to form two-dimensional layers with water 2 | Journal Name, [year], [vol], 00–00
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Fig. 3 SEM images of a) Mn (3, 5-PDC) •2H2O, b) zinc 3, 5pyridinedicarboxylate and c) cobalt 3, 5-pyridinedicarboxylate.
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SEM observations show that the as-synthesized Mn (3, 5-PDC) •2H2O is irregular particles of several micrometer in diameter, as shown in Fig. 3a. Zinc 3, 5-pyridinedicarboxylate has a morphology of clusters composed of smaller particles in Fig. 3b. While brick-like blocks for cobalt 3, 5-pyridinedicarboxylate in Fig. 3c. These hierarchical morphologies may be due to different This journal is © The Royal Society of Chemistry [year]
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TG curve (Fig. 5) shows that a two-stage loss occurs. The first loss from 20 to 200 oC is 15.42 % due to the release of H2O (Cal. 16%). While the second loss from 400 to 700 oC is ascribed to the decomposition 3, 5-pyridinedicarboxylate group with a loss of 56.15% (Cal. 58.02%). It also confirms that Mn (3, 5-PDC) • 2H2O has a high thermal stability.
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The electrochemical performance of Mn (3, 5-PDC) • 2H2O was evaculated in Fig. 6. Fig. 6a show the 1st, 2nd and 240th charge-discharge profiles at a current density of 100 mAg−1, respectively. The 1st, 2nd and 240th discharge capacities are 1066, 649.6 and 554 mAhg-1. It can be observed that they all have similar discharge profiles in shape. A small discharge platform appears around 0.4 V, implying an electrochemical reaction takes place at this potential. FT-IR spectrum of discharge products discharged at 0.1 V shows that Mn (3, 5-pdc) •2H2O has discomposed in Fig. 7. The possible decomposed products are Li2 (3, 5-PDC) • 2H2O and Mn. A possible electrochemical process might be expressed as following: Mn(3, 5-PDC) • 2H2O + 2Li+ ↔ Li2(3, 5-PDC) • 2H2O + Mn Mn (3, 5-pdc) • 2H2O also showed good cycling performance at various current densities in Fig. 6b. It shows a high discharge capacity of 583.9 mAhg-1 for the fourth cycle between a 0.05 – 3.0 V voltage limit at a discharge current density of 100 mAg-1. A capacity retention is 94.8% after 240 cycles. The 2nd and 115th discharge capacity at current densities of 300 mAg-1 are 404.8 and 310.1 mAhg-1, respectively. While the 2nd and 54th discharge capacities are 354.5 and 207.8 mAhg-1 at a current density of 750 Journal Name, [year], [vol], 00–00 | 3
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crystalline structure in Fig. 3. The structure information of coordination polymers was provided by FT-IR spectrum in Fig. 4. The complete deprotonation of 3, 5-pyridinedicarboxylic acid ligand upon reaction with metal ions was confirmed by the absence of the characteristic bands of the acid carbonyl groups at 1770 cm-1.19 The band at 1677 and 1621 cm-1 can be ascribed to the antisymmetric stretching of carboxylate groups, while the band at 1565 and 1390 cm-1 are ascribed to the characteristic stretching vibrations of the carboxylate groups .19 The diference between the asymmetric stretching vibration and the symmetric one of the carboxylate group are 116 and 227 cm-1, implying a didentate coordination mode and a monodentate coordination mode,19 respectively. The band at 3274 cm-1 can be ascribed to the coordination water.
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To make a comparison, zinc and cobalt 3, 5pyridinedicarboxylates have also been tested as anode materials for lithium-ion battery in Fig. 8. They also show similar discharge-charge profiles to that of Mn (3, 5-PDC) •2H2O, as shown in Fig. 8a, and b, respectively. But they show lower discharge capacity and worse cycling stability than Mn (3, 5-pdc) •2H2O in Fig. 8c. It can be expected that the good electrochemical performance of Mn (3, 5-PDC) •2H2O may be ascribed to the changes of crystalline structure to cobalt and zinc coordination polymers. The minor changes of electrode materials crystalline structure played a great role in good electrochemical performance for lithium and sodium-ion batteries. 20-23 In fact, nano-materials and micro-materials constructed with different nano building blocks have showed better performance for lithium and sodium-ion batteries than bulk counterparts. In our case, different metal cations have resulted in different and irregular morphologies at micrometer size without nanostructures as building blocks, which may exert little effects on the electrode properties. It can be seen that maganese dicarboxylates were apt to exhibit good cycling stability and high discharge capacity as anode materials for lithium-ion battery. It is expected that other maganese dicarboxylate is also a stable anode material for lithium-ion battery. We also prepared manganese coordination polymer [Mn (2, 5-FDC) •3H2O] (2, 5-H2FDC = 2, 54 | Journal Name, [year], [vol], 00–00
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furandicarboxylic acid) under similar procedure. A series of bands at 3345, 1586, 1544, 1416, 976, 841 and 785 cm-1 are consistent with the complex Mn (FDC) (H2O)3(H2FDC = Furan-2, 5-dicarboxylic acid) in Fig. 9.24 The band at 1586 and 1410 cm-1 can be ascribed to the asymmetric and symmetric stretching vibrations of the carboxylate groups.25The strong absorption at 3345 cm-1 is characteristic for coordination water molecules.26 The band at 3104 cm-1 can be ascribed to the aromatic C-H stretching.27 Therefore, a conclusion can be drawn that Mn (FDC) (H2O) 3 has been prepared. TG curve shows that a two-stage loss occurs in Fig. 10. The first loss from 40 to 215 oC is 20.79 % due to the release of H2O (Cal. 20.54%). Differential thermal analysis (DTA) curves show that there are one exothermic band at 172.2 oC and one endothermic band at 415.4 oC, implying that [Mn (2, 5-FDC) •3H2O] has a high thermal stability.
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mAg-1, respectively. The capacity retention are 76.6% and 58.6%, respectively. The good cycling performance might be ascribed to the reversible reaction that Mn (3, 5-pdc) •2H2O can be converted to dilithium (3, 5-pdc) •2H2O and Mn reversibly in the process of charge-discharge process. The good cycling performance was also ascribed to unique crystalline structure, which means that Mn dicarboxylate with such crystalline structure is apt to take place reversible conversion reaction as anode materials for lithium-ion battery. The cycling performance at high current densities and the high initial discharge capacity should be further improved. 3
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Fig. 10 TG curves for the managanese furandicarboxylate. The strong X-ray diffraction shows Mn (FDC) (H2O) 3 is crystalline not amorphous in Fig. 11. Those peaks were centered at 11.61, 12.99, 16.92, 21.14, 23.60, 24.78, 25.86, 26.75, 27.53, 28.61, 33.72, 36.28, 36.87, 37.85, 40.01, 41.58, 42.27, 43.94, 44.82, and 48.36o in Fig. 11a, respectively. Though they have same FT-IR spectrum and were prepared by the similar method, the coordination polymer prepared by us have a different crystalline structure to the single crystal Mn (FDC) (H2O)3 [24], as shown in Fig. 11b. SEM image shows that Mn (FDC) (H2O)3 This journal is © The Royal Society of Chemistry [year]
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has a morphology of micro-rods and micro-blocks around ten micrometers in Fig. 12.
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Fig. 11 Wide angle XRD pattern of the as-synthesized coordination polymer (a) and the wide angle XRD patterns obtained from single crystal Mn (FDC) (H2O)3 [24].
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4. Conclusions
Fig. 12 SEM image of Mn (FDC) (H2O) 3.
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In summary, coordination polymer Mn (3, 5-PDC) •2H2O and Mn 2, 5-furandicarboxylate were stable anode materials for lithium-ion batteries due to unique crystalline structure. The metal moiety of coordination polymer had a huge effect on the electrochemical performance for the formation of different crystalline structures. In addition, this facile method shed some light on metal dicarboxylate battery anode materials for lithium and sodium-ion batteries with high discharge capacity and good cycling stability.
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charge-discharge profiles at a current density of 300 mAg−1. The 1st, 3nd, 100th and 326th discharge capacities are 1355.8, 425, 424.8 and 503.2 mAhg-1, respectively. Fig. 13b shows the 1st, 2nd, 100th, 300th and 500th charge-discharge profiles at a current density of 1000 mAg−1. The 1st, 2nd, 100th, 300th and 500th discharge capacities are 1181.8, 445.4, 261.3, 306.8 and 368.1 mAhg-1, respectively. It can be seen that both have similar discharge curves with an inflexion, implying that a reversible electrochemical reaction took place at different current densities. Fig. 13c shows the Mn (2, 5-FDC) •3H2O electrode materials can steadily cycle at current densities of 100, 300, 400 and 1000 mAg-1. But the discharge capacities raised with the increasing of cycling numbers at current densities of 300, 400 and 1000 mAg-1. The Mn (2, 5-FDC) •3H2O electrode deliverers a discharge capacity up to 436.6 mAhg-1 as with 180 cycles at a current density of 100 mAg-1, 503.1 mAhg-1 as with 326 cycles at a current density of 300 mAg-1, 361.6 mAhg-1 as with 203 cycles at a current density of 400 mAg-1 and 367.7 mAhg-1 as with 500 cycles at a current density of 500 mAg-1. The Mn (2, 5-FDC) •3H2O electrode is also stable in multiple insertion/extraction processes at current densities of 100, 300, 500, 750, 1000 and 100 mAg-1, and the capacity retention is 88.1% after 60 cycles in Fig. 13d. The improvement of discharge capacity and cycling stability of maganese dicarboxylates via selecting proper dicarboxylic acids. Therefore, manganese dicarboxylates are new kinds of anode materials for lithium-ion battery as an alternative to conventional inorganic and organic electrode materials.
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The project was supported by the National Natural Science Foundation of China (Grant No. 51204058), the fund (JA12037) from the Fujian Education Department, the open project in Key Lab Adv. Energy Mat. Chem. (Nankai University) and the State Scholarship Fund from the China Scholarship Council (CSC).
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Fig. 13 The charge–discharge profiles of Mn (FDC) • 3H2O at current densities of (a) 300 mAg-1 and (b) 1000 mAg-1, the cycling performance at current densities of 100, 300, 400 and 1000 mAg-1 and (d) its corresponding evolution of the reversible capacity cycled at current densities of 100, 300, 500, 750, 1000 and 100 mAg-1 using 0.05 - 3.0 V potential window.
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The electrochemical performance of Mn (FDC) • 3H2O was shown in Fig. 13. Fig. 13a show the 1st, 3nd, 100th and 326th 75
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College of Chemistry, Fuzhou University, 2 Xueyuan Road, University Town Fuzhou, Fujian 350116, China. Tel (Fax): +86 591 87760172; Email: [email protected] b Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071. 1 F. Y. Cheng, J. Liang, Z. L. Tao and J. Chen, Adv. Mater., 2011, 23, 1695. 2 H. L. Fei, H. Li, Z. W. Li, W. J. Feng, X. Liu, and M.D. Wei, Dalton Trans., 2014, 43, 16522. 3 J. M. Tarascon, Phil. Trans. R. Soc. A, 2010 368, 3227. 4 M. Armand, S. Grugeon, H. Vezin, S. Laruelle, P. Ribière, P. Poizot, and J. M. Tarascon, Nature Mater., 2009, 8, 120.
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5 H. Kim, D. H. Seo, G. Yoon, W. A. Goddard, Y. S. Lee, W. S. Yoon, and K. Kang, J. Phys. Chem. Lett., 2014, 5, 3086. 6 N. Ogihara, T. Yasuda, Y. Kishida, T. Ohsuna, K. Miyamoto, and N. Ohba, Angew. Chem. Int. Ed., 2014, 53, 11467. 7 W. Walker, S. Grugeon, H. Vezin, S. Laruelle, M. Armand, F. Wud, and J. M. Tarascon, J. Mater. Chem., 2011, 21, 1615. 8 X. Y. Han, F. Yi, T. L. Sun, and J. T. Sun，Electrochem. Commun., 2012, 25, 136. 9 J. F. Xiang, C. X. Chang, M. Li, S. M. Wu, L. J. Yuan, and J. T. Sun, Crystal Growth & Design, 2008, 8, 280. 10 Q. Liu, L. L. Yu, Y. Wang, Y. Z. Ji, J. Horvat, M. L. Cheng, X. Y. Jia, and G.X. Wang, Inorg. Chem. 2013, 52, 2817. 11 Y. Mao, Q. Y. Kong, B. K. Guo, L. Shen, Z. X. Wang, and L. Q. Chen, Electrochimica Acta., 2013, 105, 162. 12 Y. Mao, Q. Y. Kong, B. K. Guo, X. P. Fang, X. W. Guo, L. Shen, M. Armand, Z. X. Wang, L. Q. Chen, Energy Environ. Sci., 2011, 4, 3442. 13 B. K. Guo, Q. Y. Kong, Y. Zhu, Y. Mao, Z. X. Wang, M. X. Wan, and L. Q. Chen, Chem. Eur. J., 2011, 17, 14878. 14 F. X. Sun, and G. S. Zhu, Inorg. Chem. Commun. 2013, 38, 115. 15 H. T. Xu, N. W. Zheng, H. H. Xu, Y. G. Wu, R. Y. Yang, E. Y. Ye, and X. L. Jin, J. Molecular Struc., 2002, 606, 117. 16 Y. H. Zhao, Z. M. Su, Y. M. Fu, K. Z. Shao, P. Li, Y. Wang, X. R. Hao, D. X. Zhu, and S. D. Liu, Polyhedron, 2008, 27, 583. 17 J. C. Yao, J. B. Guo, J. G. Wang, Y. F. Wang, L. Zhang, and C. P. Fan, Inorg. Chem. Commun., 2010, 13, 1178. 18 Y. L. Lu, J. Y. Wu, M. C. Chan, S. M. Huang, C. S. Lin, T. W. Chiu, Y. H. Liu, Y. S. Wen, C. H. Ueng, T. M. Chin, C. H. Hung, and K. L. Lu, Inorg. Chem. 2006, 45, 2430. 19 Q. S. Shi, S. Zhang, Q. Wang, H. W. Ma, G. Q. Yang, W. H. Sun, J. Molecular Struc., 2007, 837, 185. 20 H. L. Fei, X. Liu, Y. S. Lin, and M. D. Wei, J. Colloid Interf. Sci., 2014, 428, 73. 21 H. L. Fei, X. Liu, H. Li, and M. D. Wei, J. Colloid Interf. Sci., 2014, 418, 273. 22 H. L. Fei, Z. R. Shen, J. G. Wang, H. J. Zhou, D. T. Ding, and T. H. Chen, J. Power Sources, 2009, 2, 1164. 23 H. L. Fei, Z. R. Shen, J. G. Wang, D. T. Ding, and T. H. Chen, Electrochem. Commun., 2008, 10, 1541. 24 W. X. Chen, G. H. Wu, G. L. Zhuang, X. J. Kong, L. S. Long, R. B. Huang, and L. S. Zheng, Chem. J. Chinese U., 2011, 3, 519. 25 H. Wang, R. M. Wen, and T. L. Hu, Eur. J. Inorg. Chem., 2014, 1185. 26 X. Jiang, C. L. Jiao, Y. J. Sun, Z. B. Li, S. Liu, J. Zhang, Z. Q. Wang, L. X Sun, F. Xu, H. Y. Zhou, and Y. Sawada, J. Therm. Anal. Calorim., 2013, 112, 1579. 27 A. Nataraj, V. Balachandran, T. Karthick, M. Karabacak, and A. Atac, J. Molecular Struc., 2014, 1027, 1.
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Mangnese 3, 5-pyridinedicarboxylate anode material for Li-ion batteries showed good cycling stability.
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ARTICLE TYPE
Metal dicarboxylates: new anode materials for lithium-ion batteries with good cycling performance Hailong Fei,*a, b Xin Liu, a Zhiwei Lia, Wenjing Feng a 5
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Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX DOI: 10.1039/b000000x A simple and versatile method for preparation of manganese coordination polymer [Mn (3, 5-PDC) •2H2O] (3, 5-H2PDC = 3, 5-pyridinedicarboxylic acid) and Mn 2, 5-furandicarboxylate is developed via a simple hydrothermal route, which are firstly tested as novel high-energy anode materials for lithium-ion batteries. [Mn (3, 5-PDC) •3H2O] shows a high discharge capacity of 583.9 mAhg-1 for the fourth cycle between a 0.05 – 3.0 V voltage limit at a discharge current density of 100 mAg-1. The reversible capacity of 554.0 mAhg-1 is remained after 240 cycles with a capacity retention being 94.8%. While Mn 2, 5furandicarboxylate shows a high discharge capacity of 467.3 mAhg-1 for the second cycle. The reversible capacity of 436.6 mAhg-1 is remained after 206 cycles with a capacity retention being 93.4%.
1. Introduction 15
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Nowadays, there is a remarkable demand for rechargeable batteries with reversible and efficient electrochemical energy storage and conversion in the field of portable electronic consumer devices, electric vehicles, and large-scale electricity storage in smart and intelligent grids as renewable clean energy to lessen energy crisis.1,2 Lithium-ion battery is one of the promising rechargeable batteries for high energy density coupled with long life cycle and rate capability.3 The current concerns are driving an enormous variety of interests aimed at achieving low cost, sustainable and renewable, high safety and energy-density electrode materials for lithium-ion batteries. Bio-inspired and conjugated dicarboxylate Li2C8H4O4 (Li terephthalate) and Li2C6H4O4 (Li trans–trans-muconate) are capable of reacting with two and one extra Li per formula unit at potentials of 0.8 and 1.4 V, giving reversible capacities of 300 and 150 mAhg-1, respectively.4 Recently, other organic dicarboxylates have been widely studied as cathodes for lithium-ion batteries, such as 2, 6naphthalene dicarboxylate dilithium (2, 6-Naph (COOLi) 2), 5, 6 lithium 4, 40-tolane-dicarboxylate7 and metal-1, 4, 5, 8naphthalenetetracarboxylates.8 It is reported that several coordination polymer showed electrochemical activity for lithium-ion batteries. A Li-O bonds bridged coordination polymer Li2C6H2O4 with carbonyl groups and 2-D layered aromatic rings indicate that it can be used as cathode materials for lithium-ion batteries, but bad cycling stability was obtained.9 Manganesebased layered coordination polymer (Mn-(tfbdc)(4,4’-bpy)(H2O)2) with microporous structure was prepared by reaction of 2, 3, 5, 6tetrafluoroterephthalatic acid (H2tfbdc) and 4, 4’- bipyridine (4, 4’ - bpy) with manganese (II) acetate tetrahydrate in water solution, showing a low lithium storage capacity of 390 mAhg-1 for high molecular weight and rigid organic framework.10 polypyrrole-nickel-oxygen (PPy-Ni-O),11 PPy-Fe-O,12 and PPyThis journal is © The Royal Society of Chemistry [year]
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Co-O13 coordination complex were also reported as anode maerials for lithium-ion batteries with high capacity and good cycling performance. Transition metal dicarboxylates offer the advantages of being easy to synthesize, environmental friendly, high thermal stability, sustainable, and renewable characters. However, they have not been attracted many interests in energy conversion and storage, for example, coordination polymers based on 3, 5pyridinedicarboxylic acid. The attention mainly focused on the synthesis and crystal characterizations of Co(3,5pdc)(H2O)•(glycol), Ni(3,5-pdc)(H2O)(glycol)•(H2O) ,14 Mn (3, 5-pdc) • 2H2O15 and metal (Ni, Pb, Co) organic frameworks based on pyridine-3,5-dicarboxylic acid and two chelate ligands .16 Lanthanide (III) - cobalt (II) coordination complexes constructed with deprotonated 3, 5-pyridinedicarboxylic acid ligand,17 and Co-Cu coordination polymer with different content of water 18 were also reported. Herein, we developed a simple way to fabricate manganese, cobalt and zinc based 3, 5-pyridinedicarboxylate as well as manganese furandicarboxylate. When used as anode material for lithium-ion batteries, manganese based coordination polymer showed the highest discharge capacity and best cycling stability than cobalt and zinc based counterpart.
2. Experimental
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All chemicals are commercially available and were used as received. The preparation was performed via a hydrothermal method in an absolute alcohol - water mixed solvent. In a typical procedure, equal mmol 3, 5-pyridinedicarboxylic acid and manganese (II) acetate tetrahydrate was added to the water solution and stirred at room temperature for 2 hours. After that, the mixture was transferred to a 50-ml Teflon-lined stainless autoclave, sealed, kept at certain temperature for 24 hours, cooled to room temperature, washed with absolute alcohol and dried at
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70 OC for 12 hours. When manganese (II) acetate tetrahydrate was taken the place of by equal molar cobalt and zinc nitrates, cobalt and zinc based compounds were synthesized under the identical condition. Maganese furandicarboxylate was prepared with 2, 5-furandicarboxylic acid and manganese (II) acetate tetrahydrate under the similar condition. The morphological characteristics of the as-synthesized materials were observed with a Hitachi S-4800 field emission scanning electron microscope (SEM). X-ray diffraction (XRD) patterns were recorded on a diffractometer (Co Kα, PANalytical, and X’Pert). Thermal analysis measurements were performed using a German Netzsch DIL402C Aanalyzer. The FT-IR spectra were recorded on an America Thermo Fisher Scientific Nicolet 6700 spectrometer. A Land CT2001A battery tester was used to measure the electrode activities at room temperature. The as-synthesized coordination polymers were tested as anode materials for lithium-ion batteries. The composite of negative electrode material was consisted of the active material, a conductive material (super-pure carbon) and binder polyvinylidene difluoride (PVDF) in a weight ratio of 6/3/1. The Li metal was used as the counter electrode. The cells were charged and discharged between a 0.05 - 3.0 V voltage limit.
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molecules between the layers and the hydrogen bonds from water and carboxylic acid groups link the layers to form a three dimensional structure [15]. The corresponding coordination mode was shown in Fig. 2. It can also be seen that zinc and cobalt 3, 5pyridinedicarboxylates have similar diffraction peaks to Mn (3, 5PDC) •2H2O after 37o in Fig. 1b, and c, respectively, implying that they might have similar composition. But the diffraction peaks are very different to each other before 37o, which may be due to the different coordination essence of Mn2+, Zn2+ and Co2+ with 3, 5-pyridinedicarboxylic acid.
Fig. 2 Coordination mode of 3, 5-pyridinedicarboxylic acid.
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Fig. 1 Wide-angle powder XRD patterns of the as-synthesized coordination polymers based on different metal a) Mn, b) Zn, c) Co and d) the wide angle XRD patterns obtained from single crystal Mn (3, 5-PDC) •2H2O. Manganese 3, 5-pyridinedicarboxylic acid coordination polymer was prepared via a facile solvo-thermal method, as described in the experimental section. X-ray diffraction was performed to identify the crystalline structure in Fig. 1. The diffraction peaks are centered at 15.06, 18.4, 19.06, 23.73, 28.12, 29.07, 29.93, 34.69, 35.45, 37.36, 38.03, 38.79, 39.36, 40.12, 40.79, 41.74, 42.31, 44.51, 45.65, 46.41, 48.03, 49.56, 50.51, 51.27, 52.89, 53.46, 54.52, 56.51, 58.52 and 59.28 in Fig. 1a. It can be ascribed to the reported coordination polymer Mn (3, 5PDC) •2H2O (H2PDC= 3, 5-pyridinedicarboxylic acid) via comparing the wide angle XRD patterns of single crystal Mn (3, 5-PDC) •2H2O from ours, in which each 3,5-pdc ligand bridges three Mn (Ⅱ) centers to form two-dimensional layers with water 2 | Journal Name, [year], [vol], 00–00
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Fig. 3 SEM images of a) Mn (3, 5-PDC) •2H2O, b) zinc 3, 5pyridinedicarboxylate and c) cobalt 3, 5-pyridinedicarboxylate.
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SEM observations show that the as-synthesized Mn (3, 5-PDC) •2H2O is irregular particles of several micrometer in diameter, as shown in Fig. 3a. Zinc 3, 5-pyridinedicarboxylate has a morphology of clusters composed of smaller particles in Fig. 3b. While brick-like blocks for cobalt 3, 5-pyridinedicarboxylate in Fig. 3c. These hierarchical morphologies may be due to different This journal is © The Royal Society of Chemistry [year]
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TG curve (Fig. 5) shows that a two-stage loss occurs. The first loss from 20 to 200 oC is 15.42 % due to the release of H2O (Cal. 16%). While the second loss from 400 to 700 oC is ascribed to the decomposition 3, 5-pyridinedicarboxylate group with a loss of 56.15% (Cal. 58.02%). It also confirms that Mn (3, 5-PDC) • 2H2O has a high thermal stability.
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The electrochemical performance of Mn (3, 5-PDC) • 2H2O was evaculated in Fig. 6. Fig. 6a show the 1st, 2nd and 240th charge-discharge profiles at a current density of 100 mAg−1, respectively. The 1st, 2nd and 240th discharge capacities are 1066, 649.6 and 554 mAhg-1. It can be observed that they all have similar discharge profiles in shape. A small discharge platform appears around 0.4 V, implying an electrochemical reaction takes place at this potential. FT-IR spectrum of discharge products discharged at 0.1 V shows that Mn (3, 5-pdc) •2H2O has discomposed in Fig. 7. The possible decomposed products are Li2 (3, 5-PDC) • 2H2O and Mn. A possible electrochemical process might be expressed as following: Mn(3, 5-PDC) • 2H2O + 2Li+ ↔ Li2(3, 5-PDC) • 2H2O + Mn Mn (3, 5-pdc) • 2H2O also showed good cycling performance at various current densities in Fig. 6b. It shows a high discharge capacity of 583.9 mAhg-1 for the fourth cycle between a 0.05 – 3.0 V voltage limit at a discharge current density of 100 mAg-1. A capacity retention is 94.8% after 240 cycles. The 2nd and 115th discharge capacity at current densities of 300 mAg-1 are 404.8 and 310.1 mAhg-1, respectively. While the 2nd and 54th discharge capacities are 354.5 and 207.8 mAhg-1 at a current density of 750 Journal Name, [year], [vol], 00–00 | 3
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crystalline structure in Fig. 3. The structure information of coordination polymers was provided by FT-IR spectrum in Fig. 4. The complete deprotonation of 3, 5-pyridinedicarboxylic acid ligand upon reaction with metal ions was confirmed by the absence of the characteristic bands of the acid carbonyl groups at 1770 cm-1.19 The band at 1677 and 1621 cm-1 can be ascribed to the antisymmetric stretching of carboxylate groups, while the band at 1565 and 1390 cm-1 are ascribed to the characteristic stretching vibrations of the carboxylate groups .19 The diference between the asymmetric stretching vibration and the symmetric one of the carboxylate group are 116 and 227 cm-1, implying a didentate coordination mode and a monodentate coordination mode,19 respectively. The band at 3274 cm-1 can be ascribed to the coordination water.
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To make a comparison, zinc and cobalt 3, 5pyridinedicarboxylates have also been tested as anode materials for lithium-ion battery in Fig. 8. They also show similar discharge-charge profiles to that of Mn (3, 5-PDC) •2H2O, as shown in Fig. 8a, and b, respectively. But they show lower discharge capacity and worse cycling stability than Mn (3, 5-pdc) •2H2O in Fig. 8c. It can be expected that the good electrochemical performance of Mn (3, 5-PDC) •2H2O may be ascribed to the changes of crystalline structure to cobalt and zinc coordination polymers. The minor changes of electrode materials crystalline structure played a great role in good electrochemical performance for lithium and sodium-ion batteries. 20-23 In fact, nano-materials and micro-materials constructed with different nano building blocks have showed better performance for lithium and sodium-ion batteries than bulk counterparts. In our case, different metal cations have resulted in different and irregular morphologies at micrometer size without nanostructures as building blocks, which may exert little effects on the electrode properties. It can be seen that maganese dicarboxylates were apt to exhibit good cycling stability and high discharge capacity as anode materials for lithium-ion battery. It is expected that other maganese dicarboxylate is also a stable anode material for lithium-ion battery. We also prepared manganese coordination polymer [Mn (2, 5-FDC) •3H2O] (2, 5-H2FDC = 2, 54 | Journal Name, [year], [vol], 00–00
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furandicarboxylic acid) under similar procedure. A series of bands at 3345, 1586, 1544, 1416, 976, 841 and 785 cm-1 are consistent with the complex Mn (FDC) (H2O)3(H2FDC = Furan-2, 5-dicarboxylic acid) in Fig. 9.24 The band at 1586 and 1410 cm-1 can be ascribed to the asymmetric and symmetric stretching vibrations of the carboxylate groups.25The strong absorption at 3345 cm-1 is characteristic for coordination water molecules.26 The band at 3104 cm-1 can be ascribed to the aromatic C-H stretching.27 Therefore, a conclusion can be drawn that Mn (FDC) (H2O) 3 has been prepared. TG curve shows that a two-stage loss occurs in Fig. 10. The first loss from 40 to 215 oC is 20.79 % due to the release of H2O (Cal. 20.54%). Differential thermal analysis (DTA) curves show that there are one exothermic band at 172.2 oC and one endothermic band at 415.4 oC, implying that [Mn (2, 5-FDC) •3H2O] has a high thermal stability.
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mAg-1, respectively. The capacity retention are 76.6% and 58.6%, respectively. The good cycling performance might be ascribed to the reversible reaction that Mn (3, 5-pdc) •2H2O can be converted to dilithium (3, 5-pdc) •2H2O and Mn reversibly in the process of charge-discharge process. The good cycling performance was also ascribed to unique crystalline structure, which means that Mn dicarboxylate with such crystalline structure is apt to take place reversible conversion reaction as anode materials for lithium-ion battery. The cycling performance at high current densities and the high initial discharge capacity should be further improved. 3
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Fig. 10 TG curves for the managanese furandicarboxylate. The strong X-ray diffraction shows Mn (FDC) (H2O) 3 is crystalline not amorphous in Fig. 11. Those peaks were centered at 11.61, 12.99, 16.92, 21.14, 23.60, 24.78, 25.86, 26.75, 27.53, 28.61, 33.72, 36.28, 36.87, 37.85, 40.01, 41.58, 42.27, 43.94, 44.82, and 48.36o in Fig. 11a, respectively. Though they have same FT-IR spectrum and were prepared by the similar method, the coordination polymer prepared by us have a different crystalline structure to the single crystal Mn (FDC) (H2O)3 [24], as shown in Fig. 11b. SEM image shows that Mn (FDC) (H2O)3 This journal is © The Royal Society of Chemistry [year]
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has a morphology of micro-rods and micro-blocks around ten micrometers in Fig. 12.
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Fig. 12 SEM image of Mn (FDC) (H2O) 3.
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In summary, coordination polymer Mn (3, 5-PDC) •2H2O and Mn 2, 5-furandicarboxylate were stable anode materials for lithium-ion batteries due to unique crystalline structure. The metal moiety of coordination polymer had a huge effect on the electrochemical performance for the formation of different crystalline structures. In addition, this facile method shed some light on metal dicarboxylate battery anode materials for lithium and sodium-ion batteries with high discharge capacity and good cycling stability.
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charge-discharge profiles at a current density of 300 mAg−1. The 1st, 3nd, 100th and 326th discharge capacities are 1355.8, 425, 424.8 and 503.2 mAhg-1, respectively. Fig. 13b shows the 1st, 2nd, 100th, 300th and 500th charge-discharge profiles at a current density of 1000 mAg−1. The 1st, 2nd, 100th, 300th and 500th discharge capacities are 1181.8, 445.4, 261.3, 306.8 and 368.1 mAhg-1, respectively. It can be seen that both have similar discharge curves with an inflexion, implying that a reversible electrochemical reaction took place at different current densities. Fig. 13c shows the Mn (2, 5-FDC) •3H2O electrode materials can steadily cycle at current densities of 100, 300, 400 and 1000 mAg-1. But the discharge capacities raised with the increasing of cycling numbers at current densities of 300, 400 and 1000 mAg-1. The Mn (2, 5-FDC) •3H2O electrode deliverers a discharge capacity up to 436.6 mAhg-1 as with 180 cycles at a current density of 100 mAg-1, 503.1 mAhg-1 as with 326 cycles at a current density of 300 mAg-1, 361.6 mAhg-1 as with 203 cycles at a current density of 400 mAg-1 and 367.7 mAhg-1 as with 500 cycles at a current density of 500 mAg-1. The Mn (2, 5-FDC) •3H2O electrode is also stable in multiple insertion/extraction processes at current densities of 100, 300, 500, 750, 1000 and 100 mAg-1, and the capacity retention is 88.1% after 60 cycles in Fig. 13d. The improvement of discharge capacity and cycling stability of maganese dicarboxylates via selecting proper dicarboxylic acids. Therefore, manganese dicarboxylates are new kinds of anode materials for lithium-ion battery as an alternative to conventional inorganic and organic electrode materials.
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The project was supported by the National Natural Science Foundation of China (Grant No. 51204058), the fund (JA12037) from the Fujian Education Department, the open project in Key Lab Adv. Energy Mat. Chem. (Nankai University) and the State Scholarship Fund from the China Scholarship Council (CSC).
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Fig. 13 The charge–discharge profiles of Mn (FDC) • 3H2O at current densities of (a) 300 mAg-1 and (b) 1000 mAg-1, the cycling performance at current densities of 100, 300, 400 and 1000 mAg-1 and (d) its corresponding evolution of the reversible capacity cycled at current densities of 100, 300, 500, 750, 1000 and 100 mAg-1 using 0.05 - 3.0 V potential window.
a
65
70
The electrochemical performance of Mn (FDC) • 3H2O was shown in Fig. 13. Fig. 13a show the 1st, 3nd, 100th and 326th 75
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College of Chemistry, Fuzhou University, 2 Xueyuan Road, University Town Fuzhou, Fujian 350116, China. Tel (Fax): +86 591 87760172; Email: [email protected] b Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071. 1 F. Y. Cheng, J. Liang, Z. L. Tao and J. Chen, Adv. Mater., 2011, 23, 1695. 2 H. L. Fei, H. Li, Z. W. Li, W. J. Feng, X. Liu, and M.D. Wei, Dalton Trans., 2014, 43, 16522. 3 J. M. Tarascon, Phil. Trans. R. Soc. A, 2010 368, 3227. 4 M. Armand, S. Grugeon, H. Vezin, S. Laruelle, P. Ribière, P. Poizot, and J. M. Tarascon, Nature Mater., 2009, 8, 120.
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