Advertisement

Journal of Applied Electrochemistry

, Volume 49, Issue 3, pp 341–351 | Cite as

Preparation of Li4Ti5O12/C–C with super long high-rate cycle properties using glucose and polyurethane as double carbon sources for lithium ion batteries

  • Delai Qian
  • Yijie GuEmail author
  • Hongquan Liu
  • Yunbo Chen
  • Juan Wang
Research Article
  • 8 Downloads
Part of the following topical collections:
  1. Batteries
  2. Batteries

Abstract

Li4Ti5O12/C–C (using glucose and polyurethane as double carbon sources) microspheres with particle sizes ranging from 200 to 300 nm were fabricated with a spray drying method, followed by a solid-state reaction. Compared with pure Li4Ti5O12 and Li4Ti5O12/C (using glucose as single carbon source), Li4Ti5O12/C–C exhibits higher rate performance and better cycling properties. The initial discharge capacity of Li4Ti5O12/C–C can reach 152.6 mA h g−1 at 5.0 C, which is much higher than the discharge capacity of pure Li4Ti5O12 (124.7 mA h g−1) and Li4Ti5O12/C (141 mA h g−1). Li4Ti5O12/C–C delivers a reversible capacity of 152.1 mA h g−1 (99.7% of capacity retention) during a cycle test at 5.0 C (400 cycles). This capacity is much higher than that of pure Li4Ti5O12 (118.5 mA h g−1, 95.1%) and Li4Ti5O12/C (140 mA h g−1, 99.3%). What is more gratifying is that the discharge capacity of Li4Ti5O12/C–C is still 131 mA h g−1 after another 1600 cycles, and the Coulombic efficiency remains close to 100%, indicating the crystal structure remains stable. These excellent electrochemical properties are attributed to the different carbon content and contribution from the double carbon source coating, which increases electronic conductivity, the diffusion coefficient of lithium ions, and the effective polarization reduction.

Graphical Abstract

In our work, Li4Ti5O12/C–C exhibits excellent rate capacity and super long high-rate cycle properties by improving lithium ion diffusion coefficient (DLi) and reducing the charge transfer resistance (Rct) which comes from the higher carbon content and double carbon sources.

Keywords

Double carbon sources Lithium-ion batteries Li4Ti5O12 Polarization Super long high-rate cycle properties 

Notes

Acknowledgements

This work was financially supported by National Natural Science Foundation of China (Grant No. 51641206), Shandong Natural Science Foundation Project (Grant No. ZR2015EM013) and Special funds for independent innovation and transformation of achievements in Shandong Province (Grant No. 2014CGZ H0911).

References

  1. 1.
    Zhou K, Fan XJ, Chen W, Chen F, Wei XF, Li A, Liu JH (2017) Nitrogen-doped Li4Ti5O12/carbon hybrids derived from inorganic polymer for fast lithium storage. Electrochim Acta 247:132–138Google Scholar
  2. 2.
    Scrosati B, Hassoun J, Sun YK (2011) Lithium-ion batteries. A look into the future. Energy Environ Sci 4(9):3287–3295Google Scholar
  3. 3.
    Wang ST, Quan W, Zhu Z et al (2017) Lithium titanate hydrates with superfast and stable cycling in lithium ion batteries. Nat Commun 8(1):627Google Scholar
  4. 4.
    Lu X, Zhao L, He X et al (2012) Lithium storage in Li4Ti5O12 spinel: the full static picture from electron microscopy. Adv Mater 24(24):3233–3238Google Scholar
  5. 5.
    Zhao B, Deng X, Ran R, Liu M, Shao Z (2016) Facile Synthesis of a 3D nanoarchitectured Li4Ti5O12 electrode for ultrafast energy storage. Adv Energy Mater 6(4):1500924Google Scholar
  6. 6.
    Qi L, Chen S, Xin Y, Zhou Y, Ma Y, Zhou H (2014) Self-supported Li4Ti5O12 nanosheet arrays for lithium ion batteries with excellent rate capability and ultralong cycle life. Energy Environ Sci 7(6):1924–1930Google Scholar
  7. 7.
    Coelho J, Pokle A, Park SH, McEvoy N, Berner NC, Duesberg GS, Nicolosi V (2017) Lithium titanate/carbon nanotubes composites processed by ultrasound irradiation as anodes for lithium ion batteries. Sci Rep 7(1):7614Google Scholar
  8. 8.
    Sha Y, Zhao B, Ran R, Cai R, Shao Z (2013) Synthesis of well-crystallized Li4Ti5O12 nanoplates for lithium-ion batteries with outstanding rate capability and cycling stability. J Mater Chem A 1(42):13233–13243Google Scholar
  9. 9.
    Liu J, Wei X, Liu XW (2015) Two-dimensional wavelike spinel lithium titanate for fast lithium storage. Sci Rep 5(1):9782Google Scholar
  10. 10.
    Zhou CA, Xia XH, Wang YD, Zhong Y, Yao ZJ, Wang XL, Tu JG (2017) Rational construction of a metal core for smart combination with Li4Ti5O12 as integrated arrays with superior high-rate Li-ion storage performance. J Mater Chem A 5(4):1394–1399Google Scholar
  11. 11.
    Wang J, Zhao HL, Li ZL, Wen YT, Xia Q, Zhang Y, Yushin G (2016) Revealing rate limitations in nanocrystalline Li4Ti5O12 anodes for high-power lithium ion batteries. Adv Mater Interfaces 3(13):1600003Google Scholar
  12. 12.
    Yi TF, Yang SY, Li XY, Yao JH, Zhu YR, Zhu RS (2014) Sub-micrometric Li4−xNaxTi5O12 (0 ≤ x ≤ 0.2) spinel as anode material exhibiting high rate capability. J Power Sources 246:505–511Google Scholar
  13. 13.
    Liang Q, Cao N, Song ZH, Gao XJ, Hou LN, Guo TR, Qin X (2017) Co-doped Li4Ti5O12 nanosheets with enhanced rate performance for lithium-ion batteries. Electrochim Acta 251:407–414Google Scholar
  14. 14.
    Xu GB, Yang LW, Wei XL, Ding JW, Zhong JX, Chu PK (2015) Highly-crystalline ultrathin Li4Ti5O12 nanosheets decorated with silver nanocrystals as a high-performance anode material for lithium ion batteries. J Power Sources 295:305–313Google Scholar
  15. 15.
    Nithya VD, Selvan RK, Vediappan K, Sharmila S, Lee CW (2012) Molten salt synthesis and characterization of Li4Ti5−xMnxO12 (x = 0.0, 0.05 and 0.1) as anodes for Li-ion batteries. Appl Surf Sci 261:515–519Google Scholar
  16. 16.
    Ma Y, Ding B, Ji G, Lee JY (2013) Carbon-encapsulated F-doped Li4Ti5O12 as a high rate anode material for Li+ batteries. ACS Nano 7(12):10870–10878Google Scholar
  17. 17.
    Wang P, Zhang G, Cheng J, You Y, Li YK, Ding C, Gu JJ, Zheng XS, Zhang CF, Cao FF (2017) Facile Synthesis of carbon-coated spinel Li4Ti5O12/rutile-TiO2 composites as an improved anode material in full lithium-ion batteries with LiFePO4@N-doped carbon cathode. ACS Appl Mater Interfaces 9(7):6138–6143Google Scholar
  18. 18.
    Li J, Huang S, Li SF, Xu SJ, Pan CY (2017) Synthesis and electrochemical performance of Li4Ti5O12/Ag composite prepared by electroless plating. Ceram Int 43(2):1650–1656Google Scholar
  19. 19.
    Li X, Xu J, Huang PX et al (2016) In-situ carbon coating to enhance the rate capability of the Li4Ti5O12 anode material and suppress the electrolyte reduction decomposition on the electrode. Electrochim Acta 190:69–75Google Scholar
  20. 20.
    Guo X, Xiang HF, Zhou TP, Ju XK, Wu YC (2014) Morphologies and structures of carbon coated on Li4Ti5O12 and their effects on lithium storage performance. Electrochim Acta 130:470–476Google Scholar
  21. 21.
    Gockeln M, Pokhrel S, Meierhofer F et al (2018) Fabrication and performance of Li4Ti5O12/C Li-ion battery electrodes using combined double flame spray pyrolysis and pressure-based lamination technique. J Power Sources 374:97–106Google Scholar
  22. 22.
    Cheng L, Li XL, Liu HJ, Xiong HM, Zhang PW, Xia YY (2007) Carbon-Coated Li4Ti5O12 as a high rate electrode material for Li-ion intercalation. J Electrochem Soc 154(7):A692–A697Google Scholar
  23. 23.
    Song JJ, Sun B, Liu H, Ma ZP, Chen ZH, Shao GJ, Wang GX (2016) Enhancement of the rate capability of LiFePO4 by a new highly graphitic carbon-coating method. ACS Appl Mater Interfaces 8(24):15225–15231Google Scholar
  24. 24.
    Gu YJ, Guo Z, Liu HQ (2014) Structure and electrochemical properties of Li4Ti5O12 with Li excess as an anode electrode material for Li-ion batteries. Electrochim Acta 123:576–581Google Scholar
  25. 25.
    Wang YG, Liu HM, Wang KX, Eiji H, Wang YR, Zhou HS (2009) Synthesis and electrochemical performance of nano-sized Li4Ti5O12 with double surface modification of Ti(III) and carbon. J Mater Chem 19(37):6789–6795Google Scholar
  26. 26.
    Zhou HS, Li DL, Hibino M, Honma I (2005) A self-ordered, crystalline-glass, mesoporous nanocomposite for use as a lithium-based storage device with both high power and high energy densities. Angew Chem Int Ed 44(5):797–802Google Scholar
  27. 27.
    Zhu GN, Liu HJ, Zhuang JH, Wang CX, Wang YG, Xia YY (2011) Carbon-coated nano-sized Li4Ti5O12 nanoporous micro-sphere as anode material for high-rate lithium-ion batteries. Energy Environ Sci 4(10):4016–4022Google Scholar
  28. 28.
    Armstrong AR, Armstrong G, Canales J, Bruce PG (2004) TiO2-B nanowires. Angew Chem Int Ed 116:2286–2288Google Scholar
  29. 29.
    Gao J, Ying JR, Jiang CY, Wan CR (2007) High-density spherical Li4Ti5O12/C anode material with good rate capability for lithium ion batteries. J Power Sources 166:255–259Google Scholar
  30. 30.
    Li HS, Shen LF, Yin KB, Ji J, Wang J, Wang XY, Zhang XG (2013) Facile synthesis of N-doped carbon-coated Li4Ti5O12 microspheres using polydopamine as a carbon source for high rate lithium ion batteries. J Mater Chem A 1(24):7270–7276Google Scholar
  31. 31.
    Jeong JH, Kim MS, Choi YJ, Lee GW, Park BH, Lee SW, Roh KC, Kim KB (2018) Rational design of oxide/carbon composites to achieve superior rate-capability via enhanced lithium-ion transport across carbon to oxide. J Mater Chem A 6(14):6033–6044Google Scholar
  32. 32.
    Meng T, Yi FY, Cheng HH, Hao JN, Shu D, Zhao SX, He C, Song XN, Zhang F (2017) Preparation of lithium titanate/reduced graphene oxide composites with three-dimensional “fishnet-like” conductive structure via a gas-foaming method for high-rate lithium-ion batteries. ACS Appl Mater Interfaces 9(49):42883–42892Google Scholar
  33. 33.
    Zhang YL, Lin ZJ, Hu XB, Cao P, Wang YQ (2016) One-step solid-state synthesis of Li4Ti5O12/C with low in situ carbon content and high rate cycling performance. J Solid State Electrochem 20(1):215–223Google Scholar
  34. 34.
    Jung HG, Kim J, Scrosati B, Sun YK (2011) Micron-sized, carbon-coated Li4Ti5O12 as high power anode material for advanced lithium batteries. J Power Sources 196:7763–7766Google Scholar
  35. 35.
    Liu HP, Wen GW, Bi SF, Wang CY, Hao JM, Gao P (2016) High rate cycling performance of nanosized Li4Ti5O12/graphene composites for lithium ion batteries. Electrochim Acta 192:38–44Google Scholar
  36. 36.
    Yi TF, Yang SY, Tao M, Xie Y, Zhu YR, Zhu RS (2014) Synthesis and application of a novel Li4Ti5O12 composite as anode material with enhanced fast charge-discharge performance for lithium-ion battery. Electrochim Acta 134:377–383Google Scholar
  37. 37.
    Shenouda AY, Liu HK (2008) Electrochemical behaviour of tin borophosphate negative electrodes for energy storage systems. J Power Sources 185:1386–1391Google Scholar
  38. 38.
    Qian DL, Gu YJ, Guo SN, Liu HQ, Chen YB, Wang J, Ma GX, Wu C (2018) Effect of rich R-TiO2 on the rate and cycle properties of Li4Ti5O12 as anode for lithium ion batteries. J Energy Chem.  https://doi.org/10.1016/j.jechem.2018.07.016 Google Scholar
  39. 39.
    Li XP, Mao J (2015) A Li4Ti5O12-rutile TiO2 nanocomposite with an excellent high rate cycling stability for lithium ion batteries. New J Chem 39(6):4430–4436Google Scholar
  40. 40.
    He YB, Ning F, Li BH et al (2012) Carbon coating to suppress the reduction decomposition of electrolyte on the Li4Ti5O12 electrode. J Power Sources 202:253–261Google Scholar
  41. 41.
    Shi Y, Wen L, Li F, Cheng HM (2011) Nanosized Li4Ti5O12/graphene hybrid materials with low polarization for high rate lithium ion batteries. J Power Sources 196:8610–8617Google Scholar
  42. 42.
    Guo XF, Wan CY, Chen MM, Wang JZ, Zheng JM (2012) Carbon coating of Li4Ti5O12 using amphiphilic carbonaceous material for improvement of lithium-ion battery performance. J Power Sources 214:107–112Google Scholar
  43. 43.
    Li X, Lai C, Xiao CW, Gao XP (2011) Enhanced high rate capability of dual-phase LiTiO-TiO induced by pseudocapacitive effect. Electrochim Acta 56:9152–9158Google Scholar
  44. 44.
    Ge H, Chen L, Yuan W et al (2015) Unique mesoporous spinel Li4Ti5O12 nanosheets as anode materials for lithium-ion batteries. J Power Sources 297:436–441Google Scholar
  45. 45.
    Meng T, Zeng RH, Sun ZQ et al (2018) Chitosan-confined synthesis of N-doped and carbon-coated Li4Ti5O12 nanoparticles with enhanced lithium storage for lithium-ion batteries. J Electrochem Soc 165(5):A1046–A1053Google Scholar
  46. 46.
    Wang Y, Liao YH, Li WS, Tang XW, Li XF (2014) Carbon coating of Li4Ti5O12-TiO2 anode by using cetyl trimethyl ammonium bromide as dispersant and phenolic resin as carbon precursor. Ionics 21(6):1539–1544Google Scholar
  47. 47.
    Sheng YP, Fell CR, Son YK, Metz BZ, Jiang JW, Church BC (2014) Effect of calendering on electrode wettability in lithium-ion batteries. Front Energy Res 2(56):1–8Google Scholar
  48. 48.
    Ge H, Hao T, Osgood H, Zhang B, Chen L, Cui L, Song XM, Ogoke O, Wu G (2016) Advanced mesoporous spinel Li4Ti5O12/rGO composites with increased surface lithium storage capability for high-power lithium-ion batteries. ACS Appl Mater Interfaces 8(14):9162–9169Google Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.College of Materials Science and EngineeringShandong University of Science and TechnologyQingdaoChina
  2. 2.Advanced Manufacture Technology CenterChina Academy of Machinery Science and TechnologyBeijingChina

Personalised recommendations