Abstract
Li4Ti5O12/Li2TiO3 composite nanofibers with the mean diameter of ca. 60 nm have been synthesized via facile electrospinning. When the molar ratio of Li to Ti is 4.8:5, the Li4Ti5O12/Li2TiO3 composite nanofibers exhibit initial discharge capacity of 216.07 mAh g−1 at 0.1 C, rate capability of 151 mAh g−1 after being cycled at 20 C, and cycling stability of 122.93 mAh g−1 after 1000 cycles at 20 C. Compared with pure Li4Ti5O12 nanofibers and Li2TiO3 nanofibers, Li4Ti5O12/Li2TiO3 composite nanofibers show better performance when used as anode materials for lithium ion batteries. The enhanced electrochemical performances are explained by the incorporation of appropriate Li2TiO3 which could strengthen the structure stability of the hosted materials and has fast Li+-conductor characteristics, and the nanostructure of nanofibers which could offer high specific area between the active materials and electrolyte and shorten diffusion paths for ionic transport and electronic conduction. Our new findings provide an effective synthetic way to produce high-performance Li4Ti5O12 anodes for lithium rechargeable batteries.
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References
Armand M, Tarascon JM (2008) Building better batteries. Nature 45:652
Menachem C, Peled E, Burstein L, Rosenberg Y (1997) Characterization of modified NG7 graphite as an improved anode for lithium-ion batteries. J Power Sources 68:277
Zhang S, Xu K, Jow T (2006) Study of the charging process of a LiCoO2-based Li-ion battery. J Power Sources 160:1349
Yang S, Feng X, Müllen K (2011) Graphene-based titania nanosheets with high surface area for fast lithium storage. Adv Mater 23:3575
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
Xu H, Hu X, Sun Y, Luo W, Chen C, Liu Y, Huang Y (2014) Highly porous Li4Ti5O12/C nanofibers for ultrafast electrochemical energy storage. Nano Energy 10:163–171
Liu J, Song K, van Aken PA, Maier J, Yu Y (2014) Self-supported Li4Ti5O12–C nanotube arrays as high-rate and long-life anode materials for flexible li-ion batteries. Nano Lett 14:2597
Yi TF, Fang ZK, Xie Y, Zhu YR, Yang SY (2014) Rapid charge–discharge property of Li4Ti5O12–TiO2 nanosheet and nanotube composites as anode material for power lithium-ion batteries. ACS Appl Mater Interfaces 6:2933
Gao Y, Wang Z, Chen L (2014) Stability of spinel Li4Ti5O12 in air. J Power Sources 245:684
Pang WK, Peterson VK, Sharma N, Shiu JJ, Wu SH (2014) Lithium migration in Li4Ti5O12 studied using in situ neutron powder diffraction. Chem Mater 26:2318–2319
Kim JG, Park MS, Hwang SM, Heo YU, Liao T, Sun Z, Park JH, Kim KJ, Jeong G, Kim YJ (2014) Zr4+ doping in Li4Ti5O12 anode for lithium-ion batteries: open li+ diffusion paths through structural imperfection. ChemSusChem 7:1451
Kim JG, Shi V, Park MS, Jeong G, Heo YU, Seo M, Kim YJ, Kim JH, Dou SX (2013) Controlled Ag-driven superior rate-capability of Li4Ti5O12 anodes for lithium rechargeable batteries. Nano Res 6:365–372
Krajewski M, Michalska M, Hamankiewicz B, Ziolkowska D, Korona KP, Jasinski JB, Kaminska M, Lipinska L, Czerwinski A (2014) Li4Ti5O12 modified with Ag nanoparticles as an advanced anode material in lithium-ion batteries. J Power Sources 245:764–771
Marinaro M, Nobili F, Tossici R, Marassi R (2013) Microwave-assisted synthesis of carbon (Super-P) supported copper nanoparticles as conductive agent for Li4Ti5O12 anodes for Lithium-ion batteries. Electrochim Acta 89:555–560
Li CC, Li QH, Chen LB, Wang TH (2012) A facile titanium glycolate precursor route to mesoporous Au/Li4Ti5O12 spheres for high-rate lithium-ion batteries. ACS Appl Mater 4:1233–1238
Zhang H, Chen Y, Li J, He C, Chen Y (2014) Li4Ti5O12/CNTs composite anode material for large capacity and high-rate lithium ion batteries. Int J Hydrog Energy 39:16096–16102
Xu H, Hu X, Luo W, Sun Y, Yang Z, Hu C, Huang Y (2014) Electrospun conformal Li4Ti5O12/C fibers for high-rate lithium-ion batteries. ChemElectroChem 1:611–616
Kong RDZ, Luo WN, Yang YS, Cheng YP, Chuanwei (2014) Scalable synthesis of graphene-wrapped Li4Ti5O12 dandelion-like microspheres for lithium-ion batteries with excellent rate capability and long-cycle life. J Mater Chem A 2:20221–20230
Park H, Song T, Han H, Paik U (2013) Electrospun Li4Ti5O12 nanofibers sheathed with conductive TiN/TiOxNy layer as an anode material for high power Li-ion batteries. J Power Sources 244:726–730
Wang W, Jiang B, Xiong W, Wang Z, Jiao S (2013) A nanoparticle Mg-doped Li4Ti5O12 for high rate lithium-ion batteries. Electrochim Acta 114:198–204
Zhang Z, Cao L, Huang J, Zhou S, Huang Y, Cai Y (2013) Hydrothermal synthesis of Zn-doped Li4Ti5O12 with improved high rate properties for lithium ion batteries. Ceram Int 39:6139–6143
Wang W, Wang H, Wang S, Hu Y, Tian Q, Jiao S (2013) Ru-doped Li4Ti5O12 anode materials for high rate lithium-ion batteries. J Power Sources 228:244–249
Yang CC, Hu HC, Lin SJ, Chien WC (2014) Electrochemical performance of V-doped spinel Li4Ti5O12/C composite anode in Li-half and Li 4Ti 5O12/LiFePO4-full cell. J Power Sources 258:424–433
Zhao Z, Xu Y, Ji M, Zhang H (2013) Synthesis and electrochemical performance of F-doped Li4Ti5O12 for lithium-ion batteries. Electrochim Acta 109:645–650
Wang J, Yang Z, Li W, Zhong X, Gu L, Yu Y (2014) Nitridation Br-doped Li4Ti5O12 anode for high rate lithium ion batteries. J Power Sources 266:323–331
Lu J, Peng Q, Wang W, Nan C, Li L, Li Y (2013) Nanoscale coating of LiMO2 (M= Ni, Co, Mn) nanobelts with Li+-conductive Li2TiO3: toward better rate capabilities for li-ion batteries. J Am Chem Soc 135:1649–1652
Yang X, Yu R, Ge L, Wang D, Zhao Q, Wang X, Bai Y, Yuan H, Shu H (2014) Facile synthesis and performances of nanosized Li2TiO3-based shell encapsulated LiMn1/3Ni1/3Co1/3O2 microspheres. J Mater Chem A 2:8362–8368
Wang Y, Zhou A, Dai X, Feng L, Li J, Li J (2014) Solid-state synthesis of submicron-sized Li4Ti5O12/Li2TiO3 composites with rich grain boundaries for lithium ion batteries. J Power Sources 266:114–120
Wu X, Wen Z, Wang X, Xu X, Lin J, Song S (2010) Effect of ta-doping on the ionic conductivity of lithium titanate. Fusion Eng Des 85:1442–1445
Wu X, Wen Z, Xu X, Han J (2008) Synthesis and ionic conductivity of Mg-doped Li4Ti5O12. Solid State Ionics 179:1779–1782
Ko YW, Teh PF, Pramana SS, Wong CL, Tanto S, Li L, Madhavi S (2015) Electrospun single-phase Na1.2V3O8 materials with tunable morphologies as cathodes for rechargeable lithium- ion batteries. ChemElectroChem 2:837–846
Li ZT, Liu GX, Guo M, Ding LX, Wang SQ, Wang HH (2015) Electrospun porous vanadium pentoxide nanotubes as a high-performance cathode material for lithium-ion batteries. Electrochim Acta 173:131–138
Wee G, Soh HZ, Cheah YL, Mhaisalkar SG, Srinivasan M (2010) Synthesis and electrochemical properties of electrospun V2O5 nanofibers as supercapacitor electrodes. J Mater Chem 20:6720–6725
Teh PF, Sharma Y, Pramana SS, Srinivasan M (2011) Nanoweb anodes composed of one-dimensional, high aspect ratio, size tunable electrospun ZnFe2O4nanofibers for lithium ion batteries. J Mater Chem 21:14999–15008
Teh PF, Sharma Y, Ko YW, Pramana SS, Srinivasan M (2013) Tuning the morphology of ZnMn2O4 lithium ion battery anodes by electrospinning and its effect on electrochemical performance. RSC Adv 3:2812–2821
Kalluri S, Seng KH, Guo Z, Liu HK, Dou SX (2013) Electrospun lithium metal oxide cathode materials for lithium-ion batteries. RSC Adv 3:25576–25601
Aravindan V, Sundaramurthy J, Kumar PS, Lee Y-S, Ramakrishna S, Madhavi S (2015) Electrospun nanofibers: a prospective electro-adtive material for constructing high performance li-ion batteries. Chem Commun 51:2225–2234
Tabuchi M, Nakashima A, Shigemura H, Ado K, Kobayashi H, Sakaebe H, Tatsumi K, Kageyama H, Nakamura T, Kanno R (2003) Fine Li(4-x)/3Ti(2-2x)/3FexO2 (0.18 [less-than-or-equal] x [less-than-or-equal] 0.67) powder with cubic rock-salt structure as a positive electrode material for rechargeable lithium batteries. J Mater Chem 13:1747–1757
Morales J, Santos-Peña J, Trócoli R, Franger S (2008) Electrochemical activity of rock-salt-structured LiFeO2/Li4/3Ti2/3O2 nanocomposites in lithium cells. J Nanopart Res 10:217–226
Kim JS, Johnson CS, Thackeray MM (2002) Layered xLiMO2·(1−x)Li2MO3 electrodes for lithium batteries: a study of 0.95LiMn0.5Ni0.5O2·0.05Li2TiO3. Electrochem Commun 4:205–209
Zhang L, Wang X, Noguchi H, Yoshio M, Takada K, Sasaki T (2004) Electrochemical and ex situ XRD investigations on (1−x)LiNiO2·xLi2TiO3 (0.05≤x≤0.5). Electrochim Acta 49:3305–3311
Wang Y, Rong H, Li B, Xing L, Li X, Li W (2014) Microemulsion-assisted synthesis of ultrafine Li4Ti5O12/C nanocomposite with oleic acid as carbon precursor and particle size controller. J Power Sources 246:213–218
Huang Z, Wang D, Lin Y, Wu X, Yan P, Zhang C, He D (2014) Enhancing the high-rate performance of Li4Ti5O12 anode material for lithium-ion battery by a wet ball milling assisted solid-state reaction and ultra-high speed nano-pulverization. J Power Sources 266:60–65
Li X, Lai C, Xiao CW, Gao XP (2011) Enhanced high rate capability of dual-phase Li4Ti5O12–TiO2 induced by pseudocapacitive effect. Electrochim Acta 56:9152–9158
Haetge J, Hartmann P, Brezesinski K, Janek J, Brezesinski T (2011) Ordered large-pore mesoporous Li4Ti5O12 spinel thin film electrodes with nanocrystalline framework for high rate rechargeable lithium batteries: relationships among charge storage. Chem Mater 23:4384–4393
Zhu K, Wang Q, Kim JH, Pesaran AA, Frank AJ (2012) Pseudocapacitive lithium-ion storage in oriented anatase TiO2 nanotube arrays. J Phys Chem C 116:11895–11899
Vijayakumar M, Kerisit S, Yang Z, Graff GL, Liu J, Sears JA, Burton SD, Rosso KM, Hu J (2009) Combined 6,7Li NMR and molecular dynamics study of li diffusion in Li2TiO3. J Phys Chem C 113:20108–20116
Dorrian JF, Newnham RE (1969) Refinement of the structure of Li2TiO3. Mater Res Bull 4:179–183
Kannan A, Rabenberg L, Manthiram A (2003) High capacity surface-modified LiCoO2 cathodes for lithium-ion batteries. Electrochem Solid-State Lett 6:A16–A18
Zhang L, Noguchi H (2002) Novel layered Li–Cr–Ti–O cathode materials for lithium rechargeable batteries. Electrochem Commun 4:560–564
Du X, He W, Zhang X, Yue Y, Liu H, Zhang X, Min D, Ge X, Du Y (2012) Enhancing the electrochemical performance of lithium ion batteries using mesoporous Li3V2(PO4)3/C microspheres. J Mater Chem 22:5960–5969
Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (51573023, 50972020, 21601018), Natural Science Foundation of Jilin Province of China (20170101101JC), and Youth Foundation of Changchun University of Science and Technology (No. XQNJJ-2016-01).
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Li, S., Guo, J., Ma, Q. et al. Electrospun Li4Ti5O12/Li2TiO3 composite nanofibers for enhanced high-rate lithium ion batteries. J Solid State Electrochem 21, 2779–2790 (2017). https://doi.org/10.1007/s10008-017-3596-1
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DOI: https://doi.org/10.1007/s10008-017-3596-1