The Effect of Synthesis Parameters on the Electrochemical Performance of Li4Ti5O12

Öz

The spinel Li4Ti5O12 is synthesized by a solid-state method. The effect of the synthesis parameters including lithium content, source of Ti and grinding on the electrochemical performance of Li4Ti5O12 is investigated to optimize the crystalline size, particle size, surface area, morphology and crystallinity of the synthesized materials. The physical properties are determined by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), N2 adsoption/desorption and conductivity measurements. The electrochemical properties are investigated by conductivity and galvanostatic charge-discharge measurements. Material characterization and electrochemical measurements indicate that the best electrochemical performance can be obtained by using the Li/Ti molar ratio of 4.25/5, ball milling (BM) and anatase TiO2 (A) as starting material. Li4.25Ti5O12 A-BM, obtained via ball-mill assisted solid-state method and using anatase TiO2 as the source of Ti, exhibit the most homogeneous morphology, the least crystal and particle sizes, and highest surface area. The best-performing Li4.25Ti5O12A-BM delivers a satisfactory performance with a high charge capacity (141 mAh/g) and small capacity fading (3.6% after 30 charge-discharge cycles) at a 1 C rate (1C=175 mAh.g-1).

Anahtar Kelimeler

• Lithium-Ion Batteries
• Li4Ti5O12
• Anode Material
• Ball Mill (BM)

The Effect of Synthesis Parameters on the Electrochemical Performance of Li4Ti5O12

Öz

Spinel Li4Ti5O12, katı hal yöntemiyle sentezlenmiştir. Sentezlenen malzemelerin kristal boyutunu, partikül boyutunu, yüzey alanını, morfolojisini ve kristalliğini optimize etmek için lityum içeriği, Ti kaynağı ve öğütme gibi sentez parametrelerinin Li4Ti5O12'nin elektrokimyasal performansı üzerindeki etkisi araştırılmıştır. Fiziksel özellikler, X-ışını toz kırınımı (XRD), taramalı elektron mikroskobu (SEM), N2 adsopsiyon/desorpsiyon ve iletkenlik ölçümleri ile belirlenmiştir. Elektrokimyasal özellikler, iletkenlik ve galvanostatik şarj-deşarj ölçümleri ile araştırılmıştır. Malzeme karakterizasyonu ve elektrokimyasal ölçümler, en iyi elektrokimyasal performansın Li/Ti molar oranı 4.25/5, bilyalı öğütme (BM) ve anataz TiO2 (A) başlangıç malzemesi olarak kullanılarak elde edilebileceğini göstermektedir. Bilyalı değirmen destekli katı hal yöntemiyle ve Ti kaynağı olarak anataz TiO2 kullanılarak elde edilen Li4.25Ti5O12 A-BM, en homojen morfolojiyi, en iyi kristal ve parçacık boyutlarını ve en yüksek yüzey alanını sergiler. En iyi performans gösteren Li4.25Ti5O12 A-BM, mükemmel şarj kapasitesi (141 mAh/g) ve düşük kapasite kaybı (30 şarj-deşarj döngüsünden sonra %3,6) ile 1 C akımda (1C=175 mAh.g) tatmin edici bir performans sunar. 

Anahtar Kelimeler

• Lityum-iyon bataryalar
• Li4Ti5O12
• Anot materyali
• Bilyeli Değirmen
• Lityum-iyon bataryalar, Li4Ti5O12,Anot materyali, Bilyeli Değirmen

Kaynakça

1. 1. Z.Yang, D. Choi, S. Kerisit, K.M. Rosso, D. Wang, J. Zhang, G. Graff, J. Liu, Nanostructures and lithium electrochemical reactivity of lithium titanites and titanium oxides: A review, J Power Sources192(2009)588-598.
2. 2.T.Ohzuku, A.Ueda and N.Yamamoto, Zero‐Strain Insertion Material of Li [ Li1 / 3Ti5 / 3 ]  O 4 for Rechargeable Lithium Cells J. Electrochem. Soc.,1995, 142, 1431.
3. 3. K. Zaghib, M. Simoneau, M. Armand and M. Gauthier, Electrochemical study of Li4Ti5O12 as negative electrode for Li-ion polymer rechargeable batteries, J. Power Sources, 1999, 81, 300.
4. 4. K. Nakahara, R. Nakajima, T. Matsushima and H. Majima, Preparation of particulate Li4Ti5O12 having excellent characteristics as an electrode active material for power storage cells J. Power Sources, 2003, 117, 131.
5. 5. T.F.Yi, L.J. Jiang, J. Shu, C.B. Yue, R.S. Zhu and H.B. Qiao, Recent development and application of Li4Ti5O12 as anode material of lithium ion battery, J.Phys. Chem.Solids,2010,71,1236.
6. 6. K. Mukai, Y. Kato and H. Nakano, Understanding the Zero-Strain Lithium Insertion Scheme of Li[Li1/3Ti5/3]O4: Structural Changes at Atomic Scale Clarified by Raman Spectroscopy, J. Phys. Chem. C, 2014,118, 6, 2992–2999.
7. 7. S. Huang, Z. Wen, X. Zhu, Z. Lin, Effects of dopant on the electrochemical performance of Li4Ti5O12 as electrode material for lithium ion batteries ,Journal of Power Sources 2007, 165, 408.
8. 8. J. Gao, C. Jiang, J. Ying, C. Wan, Journal of Power Sources 2006, 155, 364.

9. 9. C.H. Chen, J.T. Vaughey, A.N. Jansen, D.W. Dees, A.J. Kahaiovn, T. Goacher, M.M. Thackeray, Studies of Mg-Substituted Li4−xMg x Ti5O12 Spinel Electrodes (0≤x≤1) for Lithium Batteries, J. Electrochem. Soc. 148 (2001) A102–A104.
10. 10. Huang, S., Wen, Z., Zhu, X., Lin, Z.: Effects of dopant on the electrochemical performance of Li4Ti5O12 as electrode material for lithium ion batteries. J. Power Sources 165, 408–412 (2007)
11. 11. Chen, C.H., Vaughey, J.T., Jansen, A.N., Dees, D.W., Kahaian, A.J., Goacher, T., Thackeray, M.M.: Studies of Mg-substituted Li4-xMgxTi5O12 spinel electrodes (0 B x B 1) for lithium batteries. J. Electrochem. Soc. 148, A102–A104 (2001)
12. 12. Wolfenstine, J., Allen, J.L.: Electrical conductivity and chargecompensation in Ta doped Li4Ti5O12. J. Power Sources 180,582–585 (2008)
13. 13.Jiang, C., Ichihara, M., Honma, I., Zhou, H.: Effect of particledispersion on high rate performance of nano-sized Li4Ti5O12 anode. Electrochim. Acta 52, 6470–6475 (2007)
14. 14.Sorensen, E.M., Barry, S.J., Jung, H.-K., Rondinelli, J.R.,Vaughey, J.T., Poeppelmeier, K.R.: Three-dimensionally ordered macroporous Li4Ti5O12: effect of wall structure on electrochemical properties. Chem. Mater. 18, 482–489 (2006)
15. 15. Bach, S., Pereira-Ramos, J.P., Baffier, N.: Electrochemical properties of sol–gel Li4/3Ti 5/3O4. J. Power Sources 81–82, 273–276 (1999)
16. 16.Y. Li, H. Zhao, Z. Tian, W. Qiu, X. Li, Solvothermal synthesis and electrochemical characterization of amorphous lithium titanate materials, J. Alloys Compd. 2008, 455, 471.
17. 17. J. Chen, L. Yang, S. Fang, Y. Tang, Synthesis of sawtooth-like Li4Ti5O12 nanosheets as anode materials for Li-ion batteries, Electrochimica Acta 2010, 55, 6596.
18. 18. Y. Tang, L. Yang, S. Fang, Z. Qiu, Li4Ti5O12 hollow microspheres assembled by nanosheets as an anode material for high-rate lithium ion batteries, Electrochimica Acta 2009, 54, 6244.
19. 19. D. K. Lee, H. W. Shim, J. S. An, C. M. Cho, I. S. Cho, K. S. Hong, D. W. Kim, Synthesis of Heterogeneous Li4Ti5O12 Nanostructured Anodes with Long-Term Cycle Stability,Nanoscale Research Letters 2010, 5, 1585.
20. 20.S. C. Lee, S. M. Lee, J. W. Lee, J. B. Lee, S. S. Han, H. C. Lee, H. J. Kim, Spinel Li4Ti5O12 Nanotubes for Energy Storage Materials, Journal of Physical Chemistry C 2009, 113, 18420.
21. 21. L. Shen, C. Yuan, H. Luo, X. Zhang, K. Xu, Y. Xia, Facile synthesis of hierarchically porous Li4Ti5O12 microspheres for high rate lithium ion batteries†, Journal of Materials Chemistry 2010, 20, 6998.
22. 22. Y. F. Tang, L. Yang, Z. Qiu, J. S. Huang, Preparation and electrochemical lithium storage of flower-like spinel Li4Ti5O12 consisting of nanosheets,Electrochemistry Communications 2008, 10, 1513.
23. 23. J. Li, Z. Tang, Z. Zhang, Controllable formation and electrochemical properties of one-dimensional nanostructured spinel Li4Ti5O12, Electrochemistry Communications 2005, 7, 894.
24. 24.Guerfi, A., Se´vigny, S., Lagace´, M., Hovington, P., Kinoshita, K., Zaghib, K.: Nano-particle Li4Ti5O12 spinel as electrode for electrochemical generators. J. Power Sources 119–121, 88–94 (2003)
25. 25. Baohua Li , Feng Ning , Yan-Bing He, Hongda Du , Quan-Hong Yang , Jun Ma , Feiyu Kang ,Chin-Tsau Hsu,Synthesis and Characterization of Long Life Li4Ti5O12/C Composite Using Amorphous TiO2 NanoparticlesInt. J. Electrochem. Sci., 6 (2011) 3210 – 3223
26. 26.Lu, H., Wang,J., Stoller, M., Wang, T., Bao, Y. ve Hao H. 2016. "An Overview of Nanomaterials for Water and Wastewater Treatment." Advances in Materials Science and Engineering 2016: 10.
27. 27. (Chemical Reviews, 2007) Ahmed H. Hammad, MSh Abdel-wahab, Sajith Vattamkandathil, Akhalakur Rahman Ansari, Structural and optical properties of ZnO thin films prepared by RF sputtering at different thicknesses. Physica B 540, 1–8 (2018))
28. 28. Cheng L, Yan J, Zhu GN, Luo JY, Wang CX, Xia YY (2010) General synthesis of carbon-coated nanostructure Li4Ti5O12 as a high rate electrode material for Li-ion intercalation. J Mater Chem 20(3):595–602
29. 29. Chang-HoonHong,Ji Heon Ryu,Jaemyung Kim, Dang-HyokYoon, Effects of the starting materials and mechanochemical activation on the properties of solid-state reacted Li4Ti5O12 for lithium ion batteries, Ceramics International 38 (2012) 301–310.
30. 30. S.W. Han et al. , Solid-state synthesis of Li4Ti5O12 for high power lithium ion battery applications Journal of Alloys and Compounds 570 (2013) 144–149.
31. 31. Prising PP, Mancini R, Petrucci L, Contini V, Villano P. , Li4Ti5O12 as anode in all-solid-state, plastic, lithium-ion batteries for low-power applications,Solid State Io2001;144:185–92.
32. 32. Li J, Jin YL, Zhang XG, Yang H., Microwave solid-state synthesis of spinel Li4Ti5O12 nanocrystallites as anode material for lithium-ion batteries,Solid State Io 2007;178:1590–4.
33. 33.Vikram Babu B, Tewodros Aregai G, Vijaya Babu K, Samatha K, Veeraiah V., Effect of Calcination Temperature on the Structural Properties of Spinel Li4Ti5O12 Anode Material for Lithium-Ion Batteries ,Chem Sci Trans 2017;6(2):1336.
34. 34. Zou, J., Gao, J., Xie, F., 2010. "An Amorphous TiO2 Sol Sensitized with H2O2 with the Enhancement of Photocatalytic Activity", Journal of Alloys and Compounds, 497: pp. 420– 427.http://dx.doi.org/10.1016/j.jallcom.2010.03.09329.
35. 35.Sean Kelly,Fred H. Pollak, and Micha Tomkiewicz,1997."Raman Spectroscopy as a Morphological Probefor TiO2 Aerogels",J. Phys. Chem. B , 101, 14, 2730–2734.
36. 36. Colthup, N., Daly, L., 1990." Wiberley, S. Introduction to Infrared and Raman Spectroscopy" Academic Press: Boston, MA, USA,. 29.
37. 37.Choi, H.C., Young, M., Seung, B., 2005. "Size effects in the Raman spectra of TiO2 nanoparticles". Vib. Spect, 37,33–38,30.
38. 38. Physical Adsorption Characterization of Nanoporous Materials, Characterization of nanoporous materials 1059 Chemie Ingenieur Technik Chemie Ingenieur Technik 2010, 82, No. 7 © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.cit-journal.de )
39. 39. Zhang, J. J. and Xia, Y. Y., Co-Sn Alloys as Negative Electrode Materials for Rechargeable Lithium Batteries, J. Electrochem. Soc, 153, A1466-1471, 2006.
40. 40. J. Liu, Y. Shen, L. Chen, Y. Wang, Y. Xia, Carbon coated Li4Ti5O12 nanowire with high electrochemical performance under elevated temperature, Electrochim. Acta 156 (2015) 38-44
41. 41. L. Wang, H. Zhang, Q. Deng, Z. Huang, A. Zhou, J. Li, Superior rate performance of Li4Ti5O12/TiO2/C/CNTs composites via microemulsion-assisted method as anodes for lithium ion battery, Electrochim. Acta 142 (2014) 202–207.
42. 42. K.T. Kim, C.-Y. Yu, C.S. Yoon, S.-J. Kim, Y.-K. Sun, S.-T. Myung, Carbon-coated Li4Ti5O12 nanowires showing high rate capability as an anode material for rechargeable sodium batteries, Nano Energy 2 (2015) 725-734. 43.Chang-Hoon Hong, Alfian Noviyanto, Ji Heon Ryu, Dang-Hyok Yoon, Jaemyung Kim, Effects of the starting materials and mechanochemical activation on the properties of solid-state reacted Li4Ti5O12 for lithium ion batteries Ceramics international,38(2012)301-310
43. 44.Wei Liu, Qian Wang, Jian Zhang, Xiaohua Xie, Haohan Liu, Guoquan Min, Baojia Xia, Isothermal kinetic analysis of the effects of high-energy ball milling on solid-state reaction of Li4Ti5O12, Powder Technology 287 (2016) 373 –379.
44. 45. Dan Wang, Xiaoyan Wu, Yaoyao Zhang, Jin Wang, Peng Yan, Chunming Zhang, Dannong He, The influence of the TiO2 particle size on the properties of Li4Ti5O12 anode material for lithium-ion battery Ceramics international 40(2014)3799-3804.
45. 46. Seung-Woo Han, Ji Heon Ryu, Joayoung Jeong, Dang-Hyok Yoon, Solid-state synthesis of Li4Ti5O12 for high power lithium ion battery applications Journal of Alloys and Compounds, 570 (2013) 144–149.
46. 47. Chih-Yuan Lin, Jenq-Gong Duh, Porous Li4Ti5O12 anode material synthesized by one-step solid state method for electrochemical properties enhancement, Journal of Alloys and Compounds 509 (2011) 3682–3685.
47. 48. Yun-Ho Jin, Kyung-Mi Min, Hyun- Woo Shim, Seung-Deok Seo, In-Sung Hwang, Kyung-Soo Park and Dong-Wan Kim, Facile synthesis of nano-Li4Ti5O12 for high-rate Li-ion battery anodes, *Nanoscale Research Letters 2012, 7:10 http://www.nanoscalereslett.com/content/7/1/10