EIS Study of the MWCNT Effect in MWCNT@TiO2 Anodes for Li-ion Batteries
Authors: Acevedo-Peña Prospero , Haro Marta , Rincón Marina E. , Bisquert Juan , García-Belmonte Germà 
Published: February 2020

Nowadays, Li-ion batteries are considered as the most prominent alternative to be used in diverse applications such portable electronic devices [1]. Nevertheless, most of the likely materials to be employed as electrodes in these cells are limited by low Li+ ion diffusion and scarce electron transport. Composite materials based on carbon nanotubes and TiO2 have shown good results for this particular application, exhibiting improved rate capability during cycling, a major drawback of pristine TiO2 [2]. Most of the electrochemical characterization of these composites have been carried out by direct current techniques, obtaining information only of the overall performance of the material, knowing few about the different steps involved during the charging-discharging process of the anode [2-6].
Herein, MWCNT@TiO2 composites were synthesized by controlled hydrolysis of titanium isopropoxide over the MWCNT [3], and the interaction between MWCNT and TiO2 in MWCNT@TiO2 anodes during the charging-discharging process was characterized with EIS in order to understand the specific role played by each material.
The TiO2 shell formed over the MWCNT was around 100 nm thick, containing 10 nm anatase crystallites. MWCNT@TiO2 shows higher capacities at every charging discharging rate with a better rate capability than pristine TiO2. The experimentally obtained EIS spectra were fitted to the equivalent circuit previously proposed for the lithiation-reaction model [7]. From the fitting it was possible to obtain information of the different processes taking place during the charge and discharge of the battery at steady-state. Two of the most representative parameters are the charge transfer resistance (Rtc) detected at high frequency, and the chemical capacity (Cµ) detected at low frequency range. The presence of MWCNT in the composite considerably diminished the Rtc of the TiO2, maintaining it at an almost constant value during the charge-discharge process. Additionally, the Cµ that is closely related to the Li+ ion storage capacity of the material, show similar values for both pristine TiO2 and MWCNT@TiO2, indicating that the Li+-ion insertion in the composite material is only taking place in the TiO2. However, it is worth mentioning that a lower potential is needed to carry the lithium ion insertion into the TiO2 lattice when it is grown over MWCNT.
The improvement in the TiO2 rate capability offered by the MWCNT@TiO2 composite seems to be related to the increase in the electronic transport, diminishing the Rtc and depolarizing the Li+ ion insertion in the TiO2. The results obtained can be extrapolated to all the family of core-shell materials based on carbon nanotubes that recently have caught the eye of different research groups working in the developing of efficient materials for Li-ion batteries [8-10].

References

Reddy, M.; Subba Rao, G.; Chowdari, B. Chem. Rev.
2013, 113, (7), 5364-5457.

Ding, S.; Chen, J. S. Adv. Funct. Mater.
2011, 21, (21), 4120-4125

Zhou, H.; Liu, L.; Wang, X.; Liang, F.; Bao, S.; Lv, D.; Tang, Y.; Jia, D. J. Mater. Chem. A
2013, 1, (30), 8525-8528

Wang, B.; Xin, H.; Li, X.; Cheng, J.; Yang, G.; Nie, F. Sci. Rep.
2014, 4, 3729

Hemalatha, K.; Prakash, A.; Guruprakash, K.; Jayakumar, M. J. Mater. Chem. A
2014, 2, (6), 1757-1766

Song, T.; Han, H.; Choi, H.; Lee, J. W.; Park, H.; Lee, S.; Park, W. I.; Kim, S.; Liu, L.; Paik, U. Nano Res.
2014, accepted

Xu, C.; Zeng, Y.; Rui, X.; Zhu, J.; Tan, H.; Guerrero, A.; Toribio, J.; Bisquert, J.; Garcia-Belmonte, G.; Yan, Q. J. Phys.
Chem. C
2013, 117, 17462−17469

Wu, Q.; Zheng, Q.; van de Krol, R. J. Phys.
Chem. C
2012, 116, (12), 7219-7226

Kiran, V.; Sampath, S. Nanoscale
2013, 5, (21), 10646-10652

Qin, G.; Xue, S.; Ma, Q.; Wang, C. CrystEngComm
2014, 16, (2), 260-269