An advanced cathode composite for co-utilization of cations and anions in lithium batteries

doi:10.1016/j.jmst.2021.05.074

Abstract

Abstract:

Anions in the electrolyte are usually ignored in conventional "rocking-chair" batteries because only cationic de-/intercalation is considered. An ingenious scheme combining LiMn_0.7Fe_0.3PO₄ (LMFP@C) and graphite as a hybrid cathode for lithium-ion batteries (LIBs) is elaborately designed in order to exploit the potential value of anions for battery performance. The hybrid cathode has a higher conductivity and energy density than any of the individual components, allowing for the co-utilization of cations and anions through the de-/intercalation of Li⁺ and PF₆^- over a wide voltage range. The optimal compound with a weight mix ratio of LMFP@C: graphite = 5: 1 can deliver the highest specific capacity of nearly 140 mA h/g at 0.1 C and the highest voltage plateau of around 4.95 V by adjusting the appropriate mixing ratio. In addition, cyclic voltammetry was used to investigate the electrode kinetics of Li⁺ and PF₆^- diffusion in the hybrid compound at various scan rates. In situ X-ray diffraction is also performed to further demonstrate the structural evolution of the hybrid cathode during the charge/discharge process.

Key words: Lithium Batteries, Cathode, Anion De-/Intercalation, Graphite, LiMn_0.7Fe_0.3PO₄

Xiao-Tong Wang, Yang Yang, Jin-Zhi Guo, Zhen-Yi Gu, Edison Huixiang Ang, Zhong-Hui Sun, Wen-Hao Li, Hao-Jie Liang, Xing-Long Wu. An advanced cathode composite for co-utilization of cations and anions in lithium batteries[J]. J. Mater. Sci. Technol., 2022, 102: 72-79.

Figures/Tables 7

Fig. 1. (a) XRD pattern of LMFP@C; (b) Raman spectrums of LMFP@C and graphite; XPS spectra of (c) Fe 2p and (d) Mn 2p for LMFP@C.

Fig. 2. (a) and (b) SEM images of LMFP@C with different magnifications; (c) TEM image of the LMFP/G hybrid compound (the insert on the top right corner is the HRTEM image of graphite at greater magnification and on the left bottom corner is the HRTEM image of LMFP@C at a higher magnification).

Fig. 3. (a) Representative GCD curves at 0.1 C rate and (b) CV curves of LMFP/G compounds with four different mixing ratios at a potential window of 2.5-5.0 V with a scan rate of 0.1 mV/s.

Fig. 4. A comparison of the (a) rate capability and (b) the Ragone plot of graphite and LMFP/G hybrid with various composition.

Fig. 5. (a-d) CV profiles of compounds of LMFP@C and graphite with different mixing ratios at various scan rate from 0.1 to 0.7 mV/s; (e-h) Linear fitting results corresponding to CV profiles describing the relationships between ip and v1/2 of the compounds in which LMFP@C and graphite are mixed in different proportions.

Fig. 6. Structural evolutions of the compounds with the mixing ratio of LMFP/graphite=1:3 during Li+/PF6- insertion/extraction process. (a) In situ XRD pattern of the compound collected at a rate of 0.2 C in the 1st cycle, with a sampling interval of 15 min. (b) Corresponding galvanostatic charge/discharge curve for the 1st cycle.

Fig. 7. Schematic illustration of the working mechanism of LMFP/G hybrid battery, in which the extraction/insertion of Li+ occurs in the low-voltage range and the insertion/extraction of PF6- happens in the high-voltage range.

References 36

[1]	C.W. Sun, S. Rajasekhara, J.B. Goodenough, F. Zhou, J. Am. Chem. Soc. 133 (2011) 2132-2135. DOI URL
[2]	Y.F. Zhao, J.C. Guo, InfoMat 2 (2020) 866-878. DOI URL
[3]	B.H. Hou, Y.Y. Wang, J.Z. Guo, Y. Zhang, Q.L. Ning, Y. Yang, W.H. Li, J.P. Zhang, X.L. Wang, X.L. Wu, ACS Appl. Mater. Interfaces 10 (2018) 3581-3589. DOI URL
[4]	X.K. Hou, W.H. Li, Y.Y. Wang, S.F. Li, Y.F. Meng, H.Y. Yu, B.K. Chen, X.L. Wu, Chin. Chem. Lett. 31 (2020) 2314-2318. DOI URL
[5]	S.S. Zhang, InfoMat 3 (2021) 125-130. DOI URL
[6]	B.H. Hou, Y.Y. Wang, Q.L. Ning, W.H. Li, X.T. Xi, X. Yang, H.J. Liang, X. Feng, X.L. Wu, Adv. Mater. 31 (2019) 1903125.
[7]	B.T. Dou, J. Yan, Q. Chen, X.G. Han, Q.M. Feng, X.M. Miao, P. Wang, Sensor. Actuat. B-Chem. 328 (2021) 129082.
[8]	Y.C. Tang, X.J. Li, H.M. Lv, W.L. Wang, C.Y. Zhi, H.F. Li, InfoMat 2 (2020) 1109-1130. DOI URL
[9]	Y.R. Ji, S.T. Weng, X.Y. Li, Q.H. Zhang, L. Gu, Rare Met 39 (2020) 205-217. DOI URL
[10]	S.P. Ong, A. Jain, G. Hautier, B. Kang, G. Ceder, Electrochem. Commun. 12 (2010) 427-430. DOI URL
[11]	J.M. Luo, E. Matios, H. Wang, X.Y. Tao, W.Y. Li, InfoMat 2 (2020) 1057-1076. DOI URL
[12]	H.J. Liang, B.H. Hou, W.H. Li, Q.L. Ning, X. Yang, Z.Y. Gu, X.J. Nie, G. Wang, X.L. Wu, Energy Environ. Sci. 12 (2019) 3575-3584. DOI URL
[13]	C.J. Cui, W.Z. Qian, Y.T. Yu, C.Y. Kong, B. Yu, L. Xiang, F. Wei, J. Am. Chem. Soc. 136 (2014) 2256-2259. DOI URL
[14]	H.P. Zhao, L. Liu, R. Vellacheri, Y. Lei, Adv. Sci. 4 (2017) 1700188.
[15]	J.N. Hao, F.H. Yang, S.L. Zhang, H.N. He, G.L. Xia, Y.J. Liu, C. Didier, T.C. Liu, W.K. Pang, V.K. Peterson, J. Lu, Z.P. Guo, Proc. Natl. Acad. Sci. U.S.A. 117 (2020) 2815-2823. DOI URL
[16]	F.P. McCullough, C.A. Levine, R.V. Snelgrove, (Dow Chemical Co.), US patent, 1989.
[17]	H.B. Wang, R.W. Wang, L.J. Liu, S. Jiang, L. Ni, X.F. Bie, X. Yang, J.G. Hu, Z.Q. Wang, H.B. Chen, L.K. Zhu, D.L. Zhang, Y.J. Wei, Z.T. Zhang, S.L. Qiu, F. Pan, Nano Energy 39 (2017) 346-354. DOI URL
[18]	S. Rothermel, P. Meister, G. Schmuelling, O. Fromm, H.W. Meyer, S. Nowak, M. Winter, T. Placke, Energy Environ. Sci. 7 (2014) 3412-3423. DOI URL
[19]	W.H. Li, Q.L. Ning, X.T. Xi, B.H. Hou, J.Z. Guo, Y. Yang, B. Chen, X.L. Wu, Adv. Mater. 31 (2019) e1804766.
[20]	J.C. Gao, S.F. Tian, Q. Li, M. Yoshio, H.Y. Wang, J. Power Sources 297 (2015) 121-126. DOI URL
[21]	P.P. Qin, M. Wang, N. Li, H.L. Zhu, X. Ding, Y.B. Tang, Adv. Mater. 29 (2017) 1606805.
[22]	H. Guo, C.Y. Wu, J. Xie, S.C. Zhang, G.S. Cao, X.B. Zhao, J. Mater. Chem. A 2 (2014) 10581-10588. DOI URL
[23]	X.N. Fu, K. Chang, L. Bao, H.W. Tang, E. Shangguan, Z.R. Chang, Electrochim. Acta 225 (2017) 272-282. DOI URL
[24]	H.X. Li, M. Xu, C.H. Gao, W. Zhang, Z.A. Zhang, Y.Q. Lai, L.F. Jiao, Energy Storage Mater. 26 (2020) 325-333.
[25]	W.J. Ren, K. Wang, J.L. Yang, R. Tan, J.T. Hu, H. Guo, Y.D. Duan, J.X. Zheng, Y. Lin, F. Pan, J. Power Sources 331 (2016) 232-239. DOI URL
[26]	D. Ding, Y. Maeyoshi, M. Kubota, J. Wakasugi, K. Kanamura, H. Abe, ACS Appl. Energy Mater. 2 (2019) 1727-1733. DOI URL
[27]	J.T. Hu, J. Yi, S.H. Cui, Y.D. Duan, T.C. Liu, G. Hua, L.P. Lin, L. Yuan, J.X. Zheng, K. Amine, F. Pan, Adv. Energy Mater. 6 (2016) 1600856.
[28]	T. Placke, G. Schmuelling, R. Kloepsch, P. Meister, O. Fromm, P. Hilbig, H.W. Meyer, M. Winter, Z. Anorg, Allg. Chem. 640 (2015) 1996-2006.
[29]	H. Guo, C.Y. Wu, L.H. Liao, J. Xie, S.C. Zhang, P.Y. Zhu, G.S. Cao, X.B. Zhao, Inorg. Chem. 54 (2015) 667-674. DOI URL
[30]	L.X. Yuan, Z.H. Wang, W.X. Zhang, X.L. Hu, J.T. Chen, Y.H. Huang, J.B. Goode-nough, Energy Environ. Sci. 4 (2011) 269-284. DOI URL
[31]	L.H. Liao, H.T. Wang, H. Guo, P.Y. Zhu, J. Xie, C.H. Jin, S.C. Zhang, G.S. Cao, T.J. Zhu, X.B. Zhao, J. Mater. Chem. A 3 (2015) 19368-19375. DOI URL
[32]	Z.Y. Gu, J.Z. Guo, Z.H. Sun, X.X. Zhao, W.H. Li, X. Yang, H.J. Liang, C.D. Zhao, X.L. Wu, Sci. Bull. 65 (2020) 702-710. DOI URL
[33]	J.Z. Guo, P.F. Wang, X.L. Wu, X.H. Zhang, Q. Yan, H. Chen, J.P. Zhang, Y.G. Guo, Adv. Mater. 29 (2017) 1701968.
[34]	J.Z. Guo, Y. Yang, D.S. Liu, X.L. Wu, B.H. Hou, W.L. Pang, K.C. Huang, J.P. Zhang, Z.M. Su, Adv. Energy Mater. 8 (2018) 1702504.
[35]	H. Liu, F.C. Strobridge, O.J. Borkiewicz, K.M. Wiaderek, K.W. Chapman, P.J. Chu-pas, C.P. Grey, Science 344 (2014) 1252817.
[36]	H.C. Shin, S.B. Park, H. Jang, K.Y. Chung, W.I. Cho, C.S. Kim, B.W. Cho, Elec-trochim. Acta 53 (2008) 7946-7951.