Abstract
Na+- and Nb5+-co-doped Li3.98Na0.02Ti4.98Nb0.02O12 (NaNbLTO), the anode material for lithium-ion batteries, is synthesized by simple solid-state reaction route at 850 °C for 12 h. Na+ is introduced into the main structure to expand the lattice, while Nb5+ increases the electronic conductivity through the reduction of some of Ti4+ ions to Ti3. The anode material is explored by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), and electric conductivity measurements. XRD patterns and FESEM images demonstrates that Na+ and Nb5+ co-doping do not alter the cubic spinel structure, the morphology, and the particle size of the Li4Ti5O12. Electric conductivity measurements reveal that the Na+- and Nb5+-co-doped NaNbLTO exhibits a higher electronic conductivity than the un-doped Li4Ti5O12 (LTO), Na+-doped Li3.98Na0.02Ti5O12 (NaLTO) and Nb5+-doped Li4Ti4.98Nb0.02O12 (NbLTO). It is found that the discharge capacity of NaNbLTO is higher than those of the un-doped LTO, Na+-doped NaLTO, and Nb5+-doped NbLTO at 0.1 C, 0.5 C, and 1.0 C current rates, which demonstrates the considerable synergic effect of Nb5+ and Na+ co-doping on improving the electrochemical performances of LTO. As evidence, NaNbLTO is a promising anode material for lithium-ion batteries.
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Armand M, Axmann P, Bresser D, Copley M, Porcher W, Trabesinger S, Wohlfahrt-Mehrens M, Zhang H (2020) Lithium-ion batteries – current state of the art and anticipated developments. J Power Sources 479:228708
Cano ZP, Banham D, Ye S, Hintennach A, Lu J, Fowler M, Chen Z (2018) Batteries and fuel cells for emerging electric vehicle markets. Nat Energy 3:279–289
Kim J-M, Zhang X, Zhang J-G, Manthiram A, Meng YS, Xu W (2021) Batteries and fuel cells for emerging electric vehicle markets. Mater Today 46:155–182
Gonzalez-Reyna MA, Rodriguez A, Perez-Robles JF (2021) One-step synthesis of carbon nanospheres with an encapsulated iron-nickel nanoalloy and its potential use as an electrocatalyst. Nanotechnology 32:095706
Zhang L, Zhang J, Xu B (2022) Enhancing the electrochemical performance of Li4Ti5O12 anode materials by codoping with Na and Br. J Alloy Compd 903:163962
Deng X, Li W, Zhu M, Xiong D, He M (2021) Synthesis of Cu-doped Li4Ti5O12 anode materials with a porous structure for advanced electrochemical energy storage: lithium-ion batteries. Solid State Ionics 364:115614
Yan B, Li MS, Li XF, Bai ZM, Yang JW, Xiong DB, Li DJ (2015) Novel understanding of carbothermal reduction enhancing electronic and ionic conductivity of Li4Ti5O12 anode. J Mater Chem A 3(22):11773–11781
Bai X, Li W, Wei A, Chang Q, Zhang LH, Liu ZF (2018) Preparation and electrochemical performance of F-doped Li4Ti5O12 for use in the lithium-ion batteries. Solid State Ion 324:13–19
Yi T-F, Wei T-T, Li Y, He Y-B, Wang Z-B (2020) Efforts on enhancing the Li-ion diffusion coefficient and electronic conductivity of titanate-based anode materials for advanced Li-ion batteries. Energy Storage Mater 26:165–197
Chen S, Xin Y, Zhou Y, Ma Y, Zhou H, Qi L (2014) Self-supported Li4Ti5O12 nanosheet arrays for lithium ion batteries with excellent rate capability and ultralong cycle life. Energy Environ Sci 7(6):1924–1930
Hong H-J, Ban G, Lee S-M, Park I-S, Lee Y-J (2020) Synthesis of 3D-structured Li4Ti5O12 from titanium(IV) oxysulfate (TiOSO4) solution as a highly sustainable anode material for lithium-ion batteries. J Alloys Compd 844:156203
Gao L, Wang L, Dai S, Cao M, Zhong Z, Shen Y, Wang M (2017) Li4Ti5O12-TiO2 nanowire arrays constructed with stacked nanocrystals for high-rate lithium and sodium ion batteries. J Power Sources 344:223–232
Chiu H-C, Lu X, Zhou J, Gu L, Reid J, Gauvin R, Zaghib K, Demopoulos GP (2017) Capacity fade mechanism of Li4Ti5O12 nanosheet anode. Adv Energy Mater 7(5):1601825
Gangaja B, Nair S, Santhanagopalan D (2019) Surface-engineered Li4Ti5O12 nanoparticles by TiO2 coating for superior rate capability and electrochemical stability at elevated temperature. Appl Surf Sci 480:817–821
Xu H, Chen J, Wang D, Xiao L, Guo X, Zhang Y, Wang Z (2017) Carbon-coated Li4Ti5O12–TiO2 microspheres as anode materials for lithium ion batteries. Surf Eng 33(7):559–566
Zhang Q, Liu Y, Lu H, Tang D, Ouyang C, Zhang L (2016) Ce3+ doped Li4Ti5O12 with CeO2 surface modification by a sol-gel method for high-performance lithiumion batteries. Electrochim Acta 189:147–157
Xu GB, Li W, 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 276:247–254
Zhu T, Yu C, Li Y, Cai R, Cui J, Zheng H, Chen D, Zhang Y, Wua Y, Wang Y (2021) Li2O-2B2O3 coating decorated Li4Ti5O12 anode for enhanced rate capability and cycling stability in lithium-ion batteries. J Colloid Interf Sci 585(574–582):575
Hou L, Qin X, Gao X, Guo T, Li X, Li J (2019) Zr-doped Li4Ti5O12 anode materials with high specific capacity for lithium-ion batteries. J Alloys Compd 774:38–45
Liang Q, Cao N, Song Z, Gao X, Hou L, Guo T, Qin X (2017) Co-doped Li4Ti5O12 nanosheets with enhanced rate performance for lithium-ion batteries. Electrochim Acta 251:407–414
Li Y, Wang Z, Zhao D, Zhang L (2015) Gd doped single-crystalline Li4Ti5O12/TiO2 nanosheets composites as superior anode material in lithium ion batteries. Electrochim Acta 182:368–375
Han J-P, Zhang B, Wang L-Y, Qi Y-X, Zhu H-L, Lu G-X, Yin L-W, Li H, Lun N, Bai Y-J (2018) Combined modification of dual-phase Li4Ti5O12–TiO2 by lithium zirconates to optimize rate capabilities and cyclability. ACS Appl Mater Interfaces 10(29):24910–24919
Zhang Y, Li J, Zhang F, Li X, Yuan B, Xia M, Zhao P, Lei R (2021) The evolution in electrochemical performance of Li4-XCaxTi5O12 (Ca doped Li4Ti5O12) as anode materials for lithium ion batteries. Colloids Surf A 616:126329
Bhatti HS, Jabeen S, Mumtaz A, Ali G, Qaisar S, Hussain S (2021) Effects of cobalt doping on structural, optical, electrical and electrochemical properties of Li4Ti5O12 anode. Journal of Alloys and Compounds 890:161691
Meng Q, Chen F, Hao Q, Lia N, Sun X (2021) Nb-doped Li4Ti5O12-TiO2 hierarchical microspheres as anode materials for high-performance Li-ion batteries at low temperature. J Alloy Compd 885:160842
VikramBabu B, SushmaReddi M, Surendra K, Rama Krishna A, Samatha K, Veeraiah V (2021) Synthesis, characterization and electrical studies of Nb-Substituted Li4Ti5O12 anode materials for Li-ion batteries. Mater Today Proc 43:1485–1490
Zhang L, Zhang J, Xu B (2022) Enhancing the electrochemical performance of Li4Ti5O12 anode materials by co-doping with Na and Br. J Alloy Compd 903:163962
Li Y, Gao H, Yang W (2022) Enhancements of the structures and electrochemical performances of Li4Ti5O12 electrodes by doping with non-metallic elements. Electrochim Acta 409:139993
Huang S, Wen Z, Gu Z, Zhu X (2005) Preparation and cycling performance of Al3+and F− co substituted compounds Li4AlxTi5−xFyO12−y. Electrochim Acta 50:4057
Du GD, Sharma N, Peterson VK, Kimpton JA, Jia DZ, Guo ZP (2011) Br-doped Li4Ti5O12 and composite TiO2 anodes for Li-ion batteries: synchrotron X-ray and in situ neutron diffraction studies. Adv Func Mater 21:3990
Kahrizi M, Ghaffarinejad A, Daneshtalab R (2021) Preparation and effects of F-doping on electrochemical properties of Li4Ti5O12 as anode material for Li-ion battery. Ionics 27:1929–1937
Lin C, Fan X, Xin Y, Cheng F, Lai MO, Zhou H, Lu L (2014) Monodispersed mesoporous Li4Ti5O12 submicrospheres as anode materials for lithium-ion batteries: morphology and electrochemical performances. Nanoscale 6:6651–6660
Liu Z, Sun L, Yang W, Yang J, Han S, Chen D, Liu Y, Liu X (2015) The synergic effects of Na and K co-doping on the crystal structure and electrochemical properties of Li4Ti5O12 as anode material for lithium ion battery. Solid State Sci 44:39–44
Xue X, Yan H, Fu Y (2019) Preparation of pure and metal-doped Li4Ti5O12 composites and their lithium-storage performances for lithium-ion batteries. Solid State Ionics 335:1–6
Shi L, Xianluo Hu, Huang Y (2014) Fast microwave-assisted synthesis of Nb-doped Li4Ti5O12 for high-rate lithium-ion batteries. J Nanopart Res 16:2332
Yi T-F, Yang S-Y, Li X-Y, Yao J-H, Zhu Y-R, Zhu R-S (2014) Sub-micrometric Li4-xNaxTi5O12 (0≥x< 0.2) spinel as anode material exhibiting high rate capability. J Power Sour 246:505–511
Wang B, Yuan F, Wang J, Wang Q, Li Z, Zhao W, Li Y, Feng J, Li W (2020) Synthesis of pomegranate-structured Si/C microspheres using P123 as surfactant for high-energy lithium-ion batteries. J Electroanal Chem 864:114102
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This work was carried out with the support of the Research Foundation of Erciyes University (Project Number FBD-10–3314). One of us, S. Rahman, also would like to thank to the Government of Turkey for the financial support during his studies at Erciyes University, Kayseri, Turkey.
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Patat, S., Rahman, S. & Dokan, F.K. The effect of sodium and niobium co-doping on electrochemical performance of Li4Ti5O12 as anode material for lithium-ion batteries. Ionics 28, 3177–3185 (2022). https://doi.org/10.1007/s11581-022-04579-3
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DOI: https://doi.org/10.1007/s11581-022-04579-3