Cobalt(II) coordination polymers as anodes for lithium-ion batteries with enhanced capacity and cycling stability

doi:10.1016/j.jmst.2017.11.006

Abstract

Abstract:

Coordination polymer Co-btca (H₄btca=1,2,4,5-benzenetetracarboxylic acid) was synthesized using a simply hydrothermal method. In particular, the as-prepared Co-btca was applied as an anode material for lithium-ion battery for the first time. Single crystal X-ray diffraction results indicated that the as-prepared Co-btca displayed unique layer structure, which was beneficial to transport Li ions and electrons. Also, owing to the porous structure and appropriate specific surface area, Co-btca electrode delivered a reversible capacity of 801.3mA h/g after 50 cycles at a current density of 200mA/g. The reversible capacity of 773.9mA h/g was maintained after 200 cycles at a current density of 500 mA/g, exhibiting enhanced cycle stability. It also showed improved rate performance, making it a promising anode material and a new choice for lithium-ion batteries.

Key words: Lithium-ion battery, Anode, Coordination polymer, Carboxylate

Yumei Luo, Lixian Sun, Fen Xu, Siyue Wei, Qingyong Wang, Hongliang Peng, Chonglin Chen. Cobalt(II) coordination polymers as anodes for lithium-ion batteries with enhanced capacity and cycling stability[J]. J. Mater. Sci. Technol., 2018, 34(8): 1412-1418.

Figures/Tables 8

Fig. 1. (a) The coordination environment of Co2+ in Co-btca (hydrogen atoms were omitted for clarity). Symmetry codes: #1: -x, -y, -z; #2: -x, y, -z; #3: x, -y, z; #4: 2-x, 1-y, 1-z for Co-btca; (b) 2D network structure of Co-btca.

Fig. 2. SEM (a, b) and TEM (c, d) images of Co-btca.

Fig. 3. As-prepared Co-btca: (a) XRD patterns of as-prepared and simulated; (b) FTIR spectra; (c) TGA curves under N2 atmosphere with a heating rate of 10?°C/min from 25 to 900?°C; (d) N2 adsorption/desorption isotherms (the inset is BJH pore-size distribution curve).

Fig. 4. Co-btca electrode: (a) CV profiles; (b) discharge/charge curves for several cycles; (c) cycled at the current density 100?mA/g; (d) cycled at the current density 200?mA/g.

Fig. 5. Cycle performance of the Co-btca electrode at the current densities of 500?mA/g (a) and 1?A/g (b).

Table 1 Comparison of the electrochemical performance of the Co-btca electrode and those of previously reported CPs electrodes.

Electrode materials	Current density (mA/g)	Initial discharge capacity (mA?h/g)	Reversible capacity (mA?h/g)	Cycles	Ref.
Zn₃(HCOO)₆	60	1344	560	60	[13]
Co₂(OH)₂BDC	50	1385	650	100	[14]
cobalt furandicarboxylate	100	1002.5	549.8	95	[17]
Cu₃(BTC)₂	96	1497	740	50	[21]
CoBTC-EtOH	100	1790.3	856	100	[27]
Mn-BTC	100	1714	694	100	[28]
Co-btca	100	1552.4	867.4	50	This work
Co-btca	500	1305.9	778.3	200	This work
Co-btca	3000	1476.8	668.4	300	This work

Fig. 6. Co-btca electrode: (a) rate performances at the current densities of 100, 300, 500, 700, 1000?mA/g; (b) EIS spectra of after 40 cycles and 100 cycles.

Scheme 1 Possible route of transporting Li ions in the layer structure of the as-prepared Co-btca. Color scheme: Co, purple; O, red; C, gray; Li, green.

References

[1]	X. Liang, Y. Yang, X. Jin, J. Cheng, J. Mater.Sci.Technol. 32(2016) 200-206.
[2]	S. Aziz, J.Q. Zhao, C. Cain, Y. Wang, J. Mater.Sci.Technol. 30(2014) 427-433.
[3]	J.L.C.Rowsell, O.M. Yaghi, Microporous Mesoporous Mat. 73(2004) 3-14.
[4]	A. Aijaz, Q. Xu, J. Phys. Chem.Lett. 5(2014) 1400-1411.
[5]	B. Xiao, Q. Yuan, Particuology 7 (2009) 129-140.
[6]	A. Corma, H. Garcia, F.X.L.I. Llabres i Xamena, Chem.Rev. 110(2010)4606-4655.
[7]	W. Liu, X.B. Yin, Trends Anal. Chem. 75(2016) 86-96.
[8]	A. Morozan, F. Jaouen, Energy Environ. Sci. 5(2012) 9269-9290.
[9]	F.S. Ke, Y.S. Wu, H. Deng, J. Solid State Chem. 223(2015) 109-121.
[10]	S.L. Li, Q. Xu, Energy Environ. Sci. 6(2013) 1656-1683.
[11]	M.R. Ryder, J.C. Tan, Mater. Sci. Technol. 30(2014) 1598-1612.
[12]	X. Li, F. Cheng, S. Zhang, J. Chen, J. Power Sources 160 (2006) 542-547.
[13]	K. Saravanan, M. Nagarathinam, P. Balaya, J.J. Vittal, J. Mater. Chem. 20(2010)8329-8335.
[14]	L. Gou, L.M. Hao, Y.X. Shi, S.L. Ma, X.Y. Fan, L. Xu, D.L. Li, K. Wang, J. Solid StateChem. 210(2014) 121-124.
[15]	Y. Zhang, Y. Niu, T. Liu, Y.L.M.Wang, J. Hou, M.Xu, Mater. Lett. 161(2015)712-715.
[16]	Q. Liu, L. Yu, Y. Wang, Y. Ji, J. Horvat, M.L. Cheng, X. Jia, G. Wang, Inorg. Chem.52(2013) 2817-2822.
[17]	H. Fei, X. Liu, Z. Li, J. Chem.Eng. 281(2015) 453-458.
[18]	C. Li, X. Hu, X. Lou, Q. Chen, B. Hu, Chem. Commun. 52(2016) 2035-2038.
[19]	H. Kumagai, C.J. Kepert, M. Kurmoo, Inorg. Chem. 41(2002) 3410-3422.
[20]	J. Zheng, J. Tian, D. Wu, M. Gu, W. Xu, C. Wang, F. Gao, M.H. Engelhard, J.-G.Zhang, J.Liu, J. Xiao, Nano Lett. 14(2014) 2345-2352.
[21]	S. Maiti, A. Pramanik, U. Manju, S. Mahanty, Microporous Mesoporous Mat.226(2016) 353-359.
[22]	C. Li, T. Chen, W. Xu, X. Lou, L. Pan, Q. Chen, B. Hu, J. Mater. Chem. A 3 (2015)5585-5591.
[23]	Y. Wang, B. Wang, F. Xiao, Z. Huang, Y. Wang, C. Richardson, Z. Chen, L. Jiao, H.Yuan, J. Power Sources 298 (2015) 203-208.
[24]	Z. Tan, Z.H. Sun, Q. Guo, H.H. Wang, D.S. Su, J. Mater.Sci.Technol. 97(2013)609-612.
[25]	X. Hu, H. Hu, C. Li, T. Li, X. Lou, Q. Chen, B. Hu, J. Solid State Chem. 242(2016)71-76.
[26]	H. Song, L. Shen, J. Wang, C. Wang, J. Mater. Chem. A 4 (2016) 15411-15419.
[27]	C. Li, X. Lou, M. Shen, X. Hu, Z. Guo, Y. Wang, B. Hu, Q. Chen, ACS Appl. Mater.Interfaces 8 (2016) 15352-15360.
[28]	S. Maiti, A. Pramanik, U. Manju, S. Mahanty, ACS Appl. Mater. Interfaces 7(2015) 16357-16363.
[29]	F. Zheng, M. He, Y. Yang, Q. Chen, Nanoscale 7 (2015) 3410-3417.
[30]	W. Guo, W. Sun, Y. Wang, Acs Nano 9 (2015) 11462-11471.
[31]	A. Banerjee, V. Aravindan, S. Bhatnagar, D. Mhamane, S. Madhavi, S. Ogale,Nano Energy 2 (2013) 890-896.
[32]	Y. Song, L. Zuo, S. Chen, J. Wu, H. Hou, L. Wang, Electrochim. Acta 173 (2015)588-594.