Hostname: page-component-cd9895bd7-fscjk Total loading time: 0 Render date: 2024-12-27T15:17:33.922Z Has data issue: false hasContentIssue false
  • English
  • Français

Structure and electrochemical performance of LiFePO4 modified with mononuclear and binuclear phthalocyanines as cathode materials

Published online by Cambridge University Press:  09 February 2017

Feifei Xu ,
Ruiqiong Wang ,
Ronglan Zhang  and
Jianshe Zhao
Feifei Xu
Affiliation:
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an, Shaanxi 710069, People’s Republic of China
Ruiqiong Wang
Affiliation:
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an, Shaanxi 710069, People’s Republic of China
Ronglan Zhang*
Affiliation:
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an, Shaanxi 710069, People’s Republic of China
Jianshe Zhao*
Affiliation:
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an, Shaanxi 710069, People’s Republic of China
*
a) Address all correspondence to these authors. e-mail: zhangrl@nwu.edu.cn
b) e-mail: jszhao@nwu.edu.cn
Get access

Abstract

Two series of lithium iron phosphate (LiFePO4) nanocomposites are prepared by a solvothermal method coupled with high temperature calcination using mononuclear and binuclear metal hexaaminophthalocyanines as modulatory additives, respectively. Physical and electrochemical performances of the composites as cathode materials of lithium-ion batteries are characterized by inductively coupled plasma (ICP), X-ray diffraction (XRD), infrared (IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical techniques. The results indicate that the as-synthesized samples modified with binuclear metal phthalocyanines can improve electrochemical properties of LiFePO4 (LFP) for lithium-ion batteries. The composite using binuclear manganese hexaaminophthalocyanine as additive can achieve the highest initial specific discharge capacity of 152.3 mAh/g at 0.1 C, higher than that of ones modified with the corresponding mononuclear phthalocyanine 143.0 mAh/g. Furthermore, the most excellent product exhibits a pretty good capacity retention of 93.0% after 50 cycles at 0.1 C, cycling stability, and low charge transfer resistance of 58.7 Ω.

Keywords

LiFePO4metal phthalocyaninescathode materiallithium-ion batteries
Type
Articles
Information
Journal of Materials Research , Volume 32 , Issue 6 , 28 March 2017 , pp. 1168 - 1176
Check for updates
Copyright
Copyright © Materials Research Society 2017 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Footnotes

Contributing Editor: Chongmin Wang

References

REFERENCES

Goodenough, J.B. and Kim, Y.: Challenges for rechargeable Li batteries. Chem. Mater. 22, 587 (2009).Google Scholar
Goodenough, J.B. and Park, K.S.: The Li-ion rechargeable battery: A perspective. J. Am. Chem. Soc. 135, 1167 (2013).Google Scholar
Devaraju, M.K. and Honma, I.: Hydrothermal and solvothermal process towards development of LiMPO4 (M = Fe, Mn) nanomaterials for lithium-ion batteries. Adv. Energy Mater. 2, 284 (2012).Google Scholar
Fan, Q., Lei, L., and Xu, X.: Direct growth of FePO4/graphene and LiFePO4/graphene hybrids for high rate Li-ion batteries. J. Power Sources 257, 65 (2013).Google Scholar
Ellis, B.L., Lee, K.T., and Nazar, L.F.: Positive electrode materials for Li-ion and Li-batteries. Chem. Mater. 22, 691 (2010).Google Scholar
Liu, T.F., Zhao, L., Zhu, J.S., Wang, B., Guo, C.F., and Wang, D.L.: Challenges for rechargeable Li batteries. Chem. Mater. 2, 2822 (2014).Google Scholar
Wang, J. and Sun, X.: Understanding and recent development of carbon coating on LiFePO4 cathode materials for lithium-ion batteries. Energy Environ. Sci. 5, 5163 (2012).Google Scholar
Zhang, H., Xu, Y., Zhao, C., Yang, X., and Jiang, Q.: Effects of carbon coating and metal ions doping on low temperature electrochemical properties of LiFePO4 cathode material. Electrochim. Acta 83, 341 (2012).Google Scholar
Li, L.X., Tang, X.C., Liu, H.T., Qu, Y., and Lu, Z.G.: Morphological solution for enhancement of electrochemical kinetic performance of LiFePO4 . Electrochim. Acta 56, 995 (2010).Google Scholar
Yamada, A., Chung, S.C., and Hinokuma, K.: Optimized LiFePO4 for lithium battery cathodes. J. Electrochem. Soc. 148, A224 (2001).Google Scholar
Xia, Y., Zhang, W.K., Huang, H., Gan, Y.P., Tian, J., and Tao, X.Y.: Self-assembled mesoporous LiFePO4 with hierarchical spindle-like architectures for high-performance lithium-ion batteries. J. Power Sources 196, 5651 (2011).Google Scholar
Praneetha, S. and Vadivel Murugan, A.: A rapid, one-pot microwave-solvothermal synthesis of a hierarchical nanostructured graphene/LiFePO4 hybrid as a high performance cathode for lithium ion batteries. RSC Adv. 3, 25403 (2013).Google Scholar
Wang, B., Xu, B., Liu, T., Liu, P., Guo, C., Wang, S., Wang, Q., Xiong, Z., Wang, D., and Zhao, X.S.: Mesoporous carbon-coated LiFePO4 nanocrystals co-modified with graphene and Mg2+ doping as superior cathode materials for lithium ion batteries. Nanoscale 6, 986 (2014).Google Scholar
Wang, R., Zhang, R., Xu, B., Yang, F., and Zhao, J.: Highly improving the electrochemical performance of LiFePO4 modified by metal phthalocyanines as cathode materials. J. Mater. Res. 30, 645 (2015).Google Scholar
Wang, R.Q., Zhang, R.L., Xu, B., Yang, F., Zhao, J.S., Zhang, S.C., and Wang, J.L.: Metal tetrabromophthalocyanines mediate the structure and electrochemical performance of lithium iron phosphate as cathode materials for lithium-ion batteries. J. Electroanal. Chem. 755, 47 (2015).Google Scholar
Ramos-Sanchez, G., Callejas-Tovar, A., Scanlon, L.G., and Balbuena, P.B.: DFT analysis of Li intercalation mechanisms in the Fe-phthalocyanine cathode of Li-ion batteries. Phys Chem Chem Phys 16, 743 (2014).Google Scholar
Zhang, R.L., Wang, R.Q., and Luo, K.: Multi-walled carbon nanotubes chemically modified by cobalt tetraaminophthalocyanines with excellent electrocatalytic activity to Li/SOCl2 battery. J. Electrochem. Soc. 161, H941 (2014).Google Scholar
Xu, B., Zhang, R.L., Wang, J.F., and Zhao, J.S.: Investigation of binuclear metal phthalocyanines as electrocatalysts for Li/SOCl2 battery. J. Solid State Electrochem. 17, 2391 (2013).Google Scholar
Wang, R., Zhang, R., Xu, B., Yang, F., and Zhao, J.: Highly improving the electrochemical performance of LiFePO4 modified by metal phthalocyanines as cathode materials. J. Mater. Res. 30, 645 (2015).Google Scholar
Qiao, Y., Pan, L., and Jia, P.: Effect of magnetic treatment on microstructure and cycle performance of LiFePO4/C cathode material. Mater. Lett. 137, 432 (2014).Google Scholar
Hairong, X., Jianqing, Z., Tao, W., Hu, G., Xiaoli, F., and Jianping, H.: Facile and economical synthesis for “plum pudding”-shaped porous LiFePO4/carbon composites for lithium ion batteries. RSC Adv. 4, 39400 (2014).Google Scholar
Xie, Y., Song, F., Xia, C., and Du, H.: Preparation of carbon-coated lithium iron phosphate/titanium nitride for a lithium-ion supercapacitor. New J. Chem. 39, 604 (2015).Google Scholar
Wang, L., He, X., and Sun, W.: Crystal orientation tuning of LiFePO4 nanoplates for high rate lithium battery cathode materials. Nano Lett. 12, 5632 (2012).Google Scholar
Di, L.F., Meligrana, G., Gerbaldi, C., Bodoardo, S., and Penazzi, N.: Surfactant-assisted mild solvothermal synthesis of nanostructured LiFePO4/C cathodes evidencing ultrafast rate capability. Electrochim. Acta 156, 188 (2015).Google Scholar
Xu, X., Xu, Y., Zhang, H., Ji, M., and Dong, H.: The effect of NiO as graphitization catalyst on the structure and electrochemical performance of LiFePO4/C cathode materials. Electrochim. Acta 158, 348 (2015).Google Scholar
Örnek, A. and Efe, O.: Doping qualifications of LiFe1−x Mg x PO4–C nano-scale composite cathode materials. Electrochim. Acta 166, 338 (2015).Google Scholar
Bai, N., Chen, H., Zhou, W., Xiang, K., Zhang, Y., Li, C., and Lu, H.: Preparation and electrochemical performance of LiFePO4/C microspheres by a facile and novel co-precipitation. Electrochim. Acta 167, 172 (2015).Google Scholar
Yamada, A., Chung, S.C., and Hinokuma, K.: Optimized LiFePO4 for lithium battery cathodes. J. Electrochem. Soc. 148, A224 (2001).Google Scholar
Aurbach, D., Zinigrad, E., Cohen, Y., and Teller, H.: A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions. Solid State Ionics 148, 405 (2002).Google Scholar
Ostrovskii, D., Ronci, F., Scrosati, B., and Jacobsson, P.: A FTIR and Raman study of spontaneous reactions occurring at the LiNi y Co(1−y)O2 electrode/non-aqueous electrolyte interface. J. Power Sources 94, 183 (2001).Google Scholar
Striebel, K.A., Sakai, E., and Cairns, E.J.: Impedance studies of the thin film LiMn2O4/electrolyte interface. J. Electrochem. Soc. 149, A61 (2002).Google Scholar
Wang, L., Sun, W., and Tang, X.: Nano particle LiFePO4 prepared by solvothermal process. J. Power Sources 244, 94 (2013).Google Scholar
Xiang, J.Y., Tu, J.P., and Zhang, L.: Improved electrochemical performances of 9LiFePO4·Li3V2(PO4)/C composite prepared by a simple solid-state method. J. Power Sources 195, 8331 (2010).Google Scholar
Muraliganth, T., Murugan, A.V., and Manthiram, A.: Nanoscale networking of LiFePO4 nanorods synthesized by a microwave-solvothermal route with carbon nanotubes for lithium ion batteries. J. Mater. Chem. 18, 5661 (2008).Google Scholar
Shu, H., Wang, X., and Wu, Q.: Improved electrochemical performance of LiFePO4/C cathode via Ni and Mn co-doping for lithium-ion batteries. J. Power Sources 237, 149 (2013).Google Scholar
Wang, X., Hao, H., Liu, J., Huang, T., and Yu, A.: A novel method for preparation of macroposous lithium nickel manganese oxygen as cathode material for lithium ion batteries. Electrochim. Acta 56, 4065 (2011).Google Scholar
Wang, X.Y., Cheng, Q., Huang, T., and Tao, A.S.: Effect of calcination atmosphere on Li/Ni disorder and electrochemical performance of layered LiNi0.5Mn0.5O2 . Acta Phys.-Chim. Sin. 27, 437 (2011).Google Scholar
Liu, H., Li, C., and Zhang, H.P.: Kinetic study on LiFePO4/C nanocomposites synthesized by solid state technique. J. Power Sources 159, 717 (2006).Google Scholar
Ji, L., Yao, Y., and Toprakci, O.: Fabrication of carbon nanofiber-driven electrodes from electrospun polyacrylonitrile/polypyrrole bicomponents for high-performance rechargeable lithium-ion batteries. J. Power Sources 195, 2050 (2010).Google Scholar
Delacourt, C., Wurm, C., and Laffont, L.: Electrochemical and electrical properties of Nb- and/or C. Solid State Ionics 177, 333 (2006).Google Scholar
Sahana, M.B., Vasu, S., Sasikala, N., Anandan, S., Sepehri-Amin, H., Sudakar, C., and Gopalan, R.: Raman spectral signature of Mn-rich nanoscale phase segregations in carbon free LiFe1−x Mn x PO4 prepared by hydrothermal technique. RSC Adv. 4, 64429 (2014).Google Scholar