Published at : 30 Oct 2019
Volume : IJtech Vol 10, No 5 (2019)
DOI : https://doi.org/10.14716/ijtech.v10i5.2563
|Bambang Priyono||Department of Metallurgy and Materials Engineering, Faculty of Engineering, Universitas Indonesia, Kampus Baru UI Depok, Depok 16424, Indonesia|
|Anne Zulfia Syahrial||Department of Metallurgy and Materials Engineering, Faculty of Engineering, Universitas Indonesia, Kampus Baru UI Depok, Depok 16424, Indonesia|
|Mohammad Ridho Nugraha||Department of Metallurgy and Materials Engineering, Faculty of Engineering, Universitas Indonesia, Kampus Baru UI Depok, Depok 16424, Indonesia|
|Dian Sepala||Department of Metallurgy and Materials Engineering, Faculty of Engineering, Universitas Indonesia, Kampus Baru UI Depok, Depok 16424, Indonesia|
|Faizah||Department of Metallurgy and Materials Engineering, Faculty of Engineering, Universitas Indonesia, Kampus Baru UI Depok, Depok 16424, Indonesia|
|Achmad Subhan||Research CaResearch Center of Physics, LIPI, PUSPIPTEK, Serpong, Tangerang Selatan, Banten 15314, Indonesiaenter for Physic, LIPI, Puspiptek, Serpong|
Lithium titanate (Li4Ti5O12 or LTO) is a very promising anode material to replace graphite in li-ion batteries due to its safety and fast-charging ability. However, due to the low theoretical capacity of LTO, a strategy must be developed to overcome this problem. Synthesizing LTO by the combined sol-gel and solid-state method, and the addition of tin powder together with activated carbon, is expected to increase the specific capacity of the anode material. The tin powder compositions in this research were 5wt%, 7.5wt% and 12.5wt%. Further, to investigate the influence of activated carbon, 5wt%, 15wt%, and 25wt% activated carbon were added, while the composition of Sn was kept at 7.5wt%. XRD, SEM and BET surface area measurements was performed to characterize the morphology and structure of the samples. The performance of the battery was analyzed using EIS, CV and CD. The results show that TiO2 rutile was present in the LTO samples, with peak rutile decreasing significantly with the addition of carbon. More disperse particle morphology was obtained by the addition of activated carbon. The LTO/Sn anode material exhibits excellent reversible capacities of 191.1 mAh/g at 12.5wt% tin. Additionally, the LTO/Sn@C has the highest specific-capacity at 270.2 mAh/g, with a composition of 5wt% carbon and 7.5wt% Sn. The results show that LTO/Sn@C is a potential anode material for the future.
Activated carbon; Anode; Li4Ti5O12/Sn; Sol-gel; Tin powder
Lithium-ion batteries (LIBs) have diverse applications, ranging from powering electronic devices such as electric vehicles (EVs), to storing renewable energy (such as solar and wind energy) (Yi et al., 2014). State-of-the-art LIBs have used graphite-based material as part of the anode component due to its desirable charge potential profile, with the discharge capacity reaching 372 mAhg-1, and lithium-insertion potential 0V (Li/Li+) (Bayati et al., 2008). However, one of the limiting factors of graphite is its low lithiation potential, poor rate-capability and solvent co-intercalation, thus limiting its potential for EV development. The process of replacing graphite with Li4Ti5O12 (LTO) has been developed to achieve optimal results. Spinel LTO is a good candidate because of its high lithium insertion voltage (1.5 VS (Li/Li+)V), excellent safety profile, cycling performance due to its zero strain insertion material (Priyono et al., 2015), and its applicability is high power conditions (Li et al., 2013). However, the specific capacity (175 mAh/g), electrical conductivity (10-13 S cm-1) and lithium diffusion coefficient (10-9 to 10-13 cm2 s-1) of LTO is low (Ariyoshi et al., 2005). One of the ways to improve the performance rate is by reducing the particle size (Syahrial et al., 2018b), coating the surface with a more conductive material, such as carbon or silver (Kim et al., 2009) or by doping (Sofyan et al., 2016). In addition, tin oxide (Sn or SnO2) can be used as the anode (Aurbach et al., 2002), whose theoretical capacity can reach up to 1491 mAhg-1. However, the expansion of volume associated with the Sn charge-discharge process reaction of the newly formed metallic Sn with lithium, which leads to the formation of Li–Sn alloys with the composition of Li4.4Sn, can reach 300% (Kim et al., 2009).
This volume expansion can lead to the collapse of the electrodes, ultimately decreasing capacity after several cycles (Crosnier et al., 2001). Several innovations have been studied by combining the nanoparticles of the Sn matrix to obtain the LTO-Sn composite (Egashira et al., 2002). In addition, increasing the surface area of the LTO-Sn composite could also be an alternative approach to improving battery performance. In this case, activated carbon is often used to increase the surface area due to its porous structure and ability to provide better support for the anode, since carbon matrices accommodate the change in volume of Sn during the charge–discharge process (Liang et al., 2011).
This paper focuses on optimizing the performance of anode batteries with LTO/Sn and LTO/Sn@C composites. The addition of Sn to LTO is aimed to increase specific capacity and reduce impedance. The LTO in this study was prepared by the sol-gel process and mixing of the Sn element using a ball-mill. Further, the addition of activated carbon is expected to produce LTO/Sn@C with evenly dispersed particles, in an effort to obtain good electrochemical performance. The effect of the tin powder and activated carbon on the LTO anode will be investigated.
The compounds LTO/Sn and LTO/Sn@C were successfully synthesized using sol-gel, the addition of activated carbon and a solid state process, while also obtaining a reasonably high surface area and minimum aggregation. There is no single phase in any of the samples resulting from more than one peak on the CV curve present. The role of the addition of Sn to LTO to form LTO/Sn succeeded in raising the capacity value of the LTO from its theoretical specific capacity of 175 mAh/g. On the other hand, in the LTO/Sn@C the influence of the addition of carbon increases the specific capacity value compared to LTO/Sn. However, the main obstacle to obtaining consistent results in this research may have been the impurities in the carbon contained in the sample, such as the presence of ash, which inhibits the flow of electrons. The CV curve shows that all the samples have more than one peak. This is consistent with the XRD results, where there are phases of TiO2, Sn and LTO in the sample. The addition of Sn and carbon generally succeeded in raising capacity. At a high C-rate, the addition of carbon raises the specific capacity value. LTO with a composition of 7.5 wt.% Sn and 5 w.t% carbon (LSC-5) creates the optimum conditions to achieve a specific capacity of 270.2 mAh/g, which is much higher than the theoretical capacity of LTO of 175 mAh/g.
The authors would like to thank the Direktorat Riset dan Pengabdian Masyarakat Universitas Indonesia (DRPM-UI) for its financial support under the Hibah PITTA grant contract number PITTA/561/FT/2018.
Abdurrahman, N.M., Priyono, B., Syahrial, A.Z., Subhan, A., 2017. Effect of Acetylene Black Content in Li4Ti5O12 Xerogel Solid-state Anode Materials on Half-cell Li-ion Batteries Performance. Journal of Physics: Conference Series, Volume 877, 012008.
Ariyoshi, K., Yamato, R., Ohzuku, T., 2005. Zero-strain Insertion Mechanism of Li[Li1/3Ti 5/3]O4 For Advanced Lithium-ion (Shuttlecock) Batteries. Electrochimica Acta, Volume 51(6), pp. 1125–1129
Aurbach, D., Nimberger, A., Markovsky, B., Levi, E., Sominski, E., Gedanken, A., 2002. Nanoparticles of SnO Produced by Sonochemistry as Anode Materials for Rechargeable Lithium Batteries. Chemistry of Material, Volume 14(7), pp. 4155–4163
Bayati, B., Babaluo, A.A., Karimi, R., 2008. Hydrothermal Synthesis of Nanostructure NaA Zeolite: The Effect of Synthesis Parameters on Zeolite Seed Size and Crystallinity. Journal of the European Ceramic Society, Volume 28(14), pp. 2653–2657
Cai, R., Yu, X., Liu, X., Shao, Z., 2010. Li4Ti5O12/Sn Composite Anodes for Lithium-ion Batteries: Synthesis and Electrochemical Performance. Journal of Power Sources, Volume 195(24), pp. 8244–8250
Chen, M., Bae, J., 2006. Preparation of Carbon-Coated TiO2 at Different Heat Treatment Temperatures and Their Photoactivity. Carbon Science, Volume 7(4), pp. 259–265
Crosnier, O., Brousse, T., Devaux, X., Fragnaud, P., Schleich, D.M., 2001. New Anode Systems for Lithium Ion Cells. Journal of Power Sources, Volume 94(2), pp. 169–174
Egashira, M., Takatsuji, H., Okada, S., Yamaki, J.I., 2002. Properties of Containing Sn Nanoparticles Activated Carbon Fiber for a Negative Electrode in Lithium Batteries. Journal of Power Sources, Volume 107(1), pp. 56–60
Fang, W., Zuo, P., Ma, Y., Cheng, X., Liao, L., Yin, G., 2013. Facile Preparation of Li4Ti5O12/AB/MWCNTs Composite with High-rate Performance for Lithium Ion Battery. Electrochimica Acta, Volume 94, pp. 294–299
Kim, Y., Yoon, Y., Shin, D., 2009. Fabrication of Sn/SnO2 Composite Powder for Anode of Lithium Ion Battery by Aerosol Flame Deposition. Journal of Analytical and Applied Pyrolysis, Volume 85(1–2), pp. 557–560
Li, B., Ning, F., He, Y., Du, H., Yang, Q., Kang, F., Hsu, C., 2011. Synthesis and Characterization of Long Life Li4Ti5O12/C Composite using Amorphous TiO2 Nanoparticles. International Journal of Electrochemical Science, Volume 6, pp. 3210–3223
Li, H., Shen, L., Zhang, X., Wang, J., Nie, P., Che, Q., Ding, B., 2013. Nitrogen-doped Carbon Coated Li4Ti5O12 Nanocomposite: Superior Anode Materials for Rechargeable Lithium Ion Batteries. Journal of Power Sources, Volume 221, pp. 122–127
Liang, S., Zhu, X., Lian, P., Yang, W., Wang, H., 2011. Superior Cycle Performance of Sn@C/graphene Nanocomposite as an Anode Material for Lithium-ion Batteries. Journal of Solid State Chemistry, Volume 184(6), pp. 1400–1404
Lübke, M., Johnson, I., Makwana, N.M., Brett, D., Shearing, P., Liu, Z., Darr, J.A., 2015. High Power TiO2 and High Capacity Sn-doped TiO2 Nanomaterial Anodes for Lithium-ion Batteries. Journal of Power Sources, Volume 294, pp. 94–102
Priyono, B., Syahrial, A.Z., Yuwono, A.H., Kartini, E., Marfelly, M., Rahmatulloh, W.M.F., 2015. Synthesis of Lithium Titanate (Li4Ti5O12) through Hydrothermal Process by using Lithium Hydroxide (LiOH) and Titanium Dioxide (TiO2) Xerogel. International Journal of Technology, Volume 6(4), pp. 555–564
Sivashanmugam, A., Kumar, T.P., Renganathan, N.G., Gopukumar, S., Wohlfahrt-Mehrens, M., Garche, J., 2005. Electrochemical Behavior of Sn/SnO2 Mixtures for Use as Anode in Lithium Rechargeable Batteries. Journal of Power Sources, Volume 144(1), pp. 197–203
Sofyan, N., Putro, D.Y., and Zulfia, A., 2016. Performance of Vanadium-doped LiFePO4/C Used as a Cathode for a Lithium Ion Battery. International Journal of Technology, Volume 7(8), pp. 1225–1235
Sun, X., Hegde, M., Zhang, Y., He, M., Gu, L., Wang, Y., Shu, J., Radovanovic, P.V., Cui, B., 2014. Structure and Electrochemical Properties of Spinel Li4Ti5O12 Nanocomposites as Anode for Lithium-ion Battery. International Journal of Electrochemical Science, Volume 9(4), pp. 1583–1596
Syahrial, A.Z., Aldy, F., Priyono, B., Subhan, A., 2018a. Enhanced Electrochemical Performances of Li4Ti5O12/Sn Composites Anode via Sol-hydrothermal Method for Lithium Ion Batteries. IOP Conference Series: Earth and Environmental Science, Volume 105
Syahrial, A.Z., Margaretha, Y.R., Priyono, B., Subhan, A., 2018b. Synthesis of LTO Nanorods with AC/Nano-Si Composites as Anode Materials for Lithium-ion Batteries. International Journal of Technology, Volume 9(6), pp. 1225–1235
Yi, T.-F., Yang, S.-Y., Tao, M., Xie, Y., Zhu, Y.-R., Zhu, R.-S., 2014. Synthesis and Application of a Novel Li4Ti5O12 Composite as Anode Material with Enhanced Fast Charge-discharge Performance for Lithium-ion Battery. Electrochimica Acta, Volume 134, pp. 377–383
Zhao, B., Ran, R., Liu, M., Shao, Z., 2015. A Comprehensive Review of Li4Ti5O12-based Electrodes for Lithium-ion Batteries: The Latest Advancements and Future Perspectives. Materials Science & Engineering: Reports, Volume 98, pp. 1–71