, Volume 24, Issue 10, pp 2925–2934 | Cite as

Anatase TiO2 nanoparticles for lithium-ion batteries

  • S. S. El-Deen
  • A. M. Hashem
  • A. E. Abdel Ghany
  • S. Indris
  • H. Ehrenberg
  • A. Mauger
  • C. M. JulienEmail author
Original Paper


Anatase TiO2 nanoparticles were prepared by a simple sol-gel method at moderate temperature. X-ray powder diffraction (XRD) and Raman spectroscopy revealed the exclusive presence of anatase TiO2 without impurities such as rutile or brookite TiO2. Thermogravimetric analysis confirmed the formation of TiO2 at about 400 °C. Particle size of about 20 nm observed by transmission electron microscopy matches well with the dimension of crystallites calculated from XRD. The electrochemical tests of the sol-gel-prepared anatase TiO2 show promising results as electrode for lithium-ion batteries with a stable specific capacity of 174 mAh g−1 after 30 cycles at C/10 rate. The results show that improvement of the electrochemical properties of TiO2 to reach the performance required for use as an electrode for lithium-ion batteries requires not only nanosized porous particles but also a morphology that prevents the self-aggregation of the particles during cycling.


TiO2 anatase Nanoparticles Raman spectroscopy Electrode material Lithium-ion batteries 


  1. 1.
    Han B, Kim KJ, Hwang BM, Kim SB, Park KW (2013) Single-crystalline rutile TiO2 nanowires for improved lithium ion intercalation properties. J Power Sources 222:225–229. CrossRefGoogle Scholar
  2. 2.
    Liu CL, Wang Y, Zhang C, Li XS, Dong WS (2014) In situ synthesis of α-MoO3/graphene composites as anode materials for lithium ion battery. Mater Chem Phys 143(3):1111–1118. CrossRefGoogle Scholar
  3. 3.
    Julien CM, Mauger A, Vijh A, Zaghib K (2016) Lithium batteries: science and technology. Springer, Cham, 630 pages. CrossRefGoogle Scholar
  4. 4.
    Doh CH, Kim DH, Kim HS, Shin HM, Jeong YD, Moon SI, Jin BS, Eom SW, Kim HS, Kim KW, Oh DH, Veluchamy A (2008) Thermal and electrochemical behavior of C/LixCoO2 cell during safety test. J Power Sources 175(2):881–885. CrossRefGoogle Scholar
  5. 5.
    Endo M, Kim C, Nishimura K, Fujino T, Miyashita K (2000) Recent development of carbon materials for Li ion batteries. Carbon 38(2):183–197. CrossRefGoogle Scholar
  6. 6.
    Qiao H, Xiao L, Zhang L (2008) Phosphatization: a promising approach to enhance the performance of mesoporous TiO2 anode for lithium ion batteries. Electrochem Commun 10(4):616–620. CrossRefGoogle Scholar
  7. 7.
    Huang XH, Tu JP, Zhang CQ, Xiang JY (2007) Net-structured NiO–C nanocomposite as Li-intercalation electrode material. Electrochem Commun 9(5):1180–1184. CrossRefGoogle Scholar
  8. 8.
    Oh SW, Bang HJ, Bae YC, Sun YK (2007) Effect of calcination temperature on morphology, crystallinity and electrochemical properties of nano-crystalline metal oxides (Co3O4, CuO, and NiO) prepared via ultrasonic spray pyrolysis. J Power Sources 173(1):502–509. CrossRefGoogle Scholar
  9. 9.
    Chen G, Rodriguez R, Fei L, Xu Y, Deng S, Smirnov S, Luo H (2014) A facile hydrothermal route to iron(III) with conductive additives as composite anode for lithium ion batteries. J Power Sources 259:227–232. CrossRefGoogle Scholar
  10. 10.
    Xu Y, Jian G, Liu Y, Zhu Y, Zachariah MR, Wang C (2014) Superior electrochemical performance and structure evolution of mesoporous Fe2O3 anodes for lithium-ion batteries. Nano Energy 3:26–35. CrossRefGoogle Scholar
  11. 11.
    Oh HD, Lee SW, Kim SO, Lee JK (2013) Facile synthesis of carbon layer-entangled Fe2O3 clusters as anode materials for improved Li-ion batteries. J Power Sources 244:575–580. CrossRefGoogle Scholar
  12. 12.
    Jiang Y, Zhang D, Li Y, Yuan T, Bahlawane N, Liang C, Sun W, Lu Y, Yan M (2014) AmorphousFe2O3 as a high-capacity, high-rate and long-life anode material for lithium ion batteries. Nano Energy 4:23–30. CrossRefGoogle Scholar
  13. 13.
    Casino S, Di Lupo F, Francia C, Tuel A, Bodoardo S, Gerbaldi C (2014) Surfactant-assisted sol gel preparation of high-surface area mesoporous TiO2 nanocrystalline Li-ion battery anodes. J Alloys Compd 594:114–121. CrossRefGoogle Scholar
  14. 14.
    Di Lupo F, Tuel A, Mendez V, Francia C, Meligrana G, Bodoardo S, Gerbaldi C (2014) Mesoporous TiO2 nanocrystals produced by a fast hydrolytic process as high-rate long-lasting Li-ion battery anodes. Acta Mater 69:60–67. CrossRefGoogle Scholar
  15. 15.
    Wang D, Wu X, Zhang Y, Wang J, Yan P, Zhang C, He D (2014) The influence oftheTiO2 particle size on the properties of Li4Ti5O12 anode material for lithium-ion battery. Ceram Int 40(2):3799–3804. CrossRefGoogle Scholar
  16. 16.
    Usui H, Wasada K, Shimizu M, Sakaguchi H (2013) TiO2/Si composites synthesized by sol–gel method and their improved electrode performance as Li-ion battery anodes. Electrochim Acta 111:575–580. CrossRefGoogle Scholar
  17. 17.
    Yan Y, Wang J, Chang Q, Babikier M, Wang H, Li H, Yu Q, Gao S, Jiao S (2013) Fabrication of mesoporous TiO2 electrodes by chemical technique for dye-sensitized solar cells. Electrochim Acta 94:277–284. CrossRefGoogle Scholar
  18. 18.
    Chen CL, Chang TW, Su SC, Teng H, Lee YL (2014) High performance solid-state dye-sensitized solar cells based on poly(acrylonitrile-co-vinyl acetate)/TiO2 nanoparticles redox electrolytes. J Power Sources 247:406–411. CrossRefGoogle Scholar
  19. 19.
    Hong CK, Jung YH, Kim HJ, Park KH (2014) Electrochemical properties of TiO2 nanoparticle/nanorod composite photoanode for dye-sensitized solar cells. Curr Appl Phys 14(3):294–299. CrossRefGoogle Scholar
  20. 20.
    Xiong J, Yang B, Zhou C, Yang J, Duan H, Huang W, Zhang X, Xia X, Zhang L, Huang H, Gao Y (2014) Enhanced efficiency and stability of polymer solar cells with TiO2 nanoparticles buffer layer. Org Electron 15(4):835–843. CrossRefGoogle Scholar
  21. 21.
    Umar AA, Nafisah S, Saad SKM, Tan ST, Balouch A, Salleh M, Oyama M (2014) Pori ferous microtablet of anatase TiO2 growth on an ITO surface for high efficiency dye-sensitized solar cells. Sol Energy Mater Sol Cells 122:174–182. CrossRefGoogle Scholar
  22. 22.
    Zhang S, Zhang S, Peng B, Wang H, Yu H, Wang H, Peng F (2014) High performance hydrogenated TiO2 nanorod arrays as a photoelectrochemical sensor for organic compounds under visible light. Electrochem Commun 40:24–27. CrossRefGoogle Scholar
  23. 23.
    Lee HU, Lee SC, Lee SM, Lee JW, Kim HJ, Lee J (2013) Improved photocatalytic and antibacterial activities of three-dimensional polycrystalline anatase TiO2 photocatalysts. Appl Catal A 467:394–399. CrossRefGoogle Scholar
  24. 24.
    Lee AC, Lin RH, Yang CY, Lin MH, Wang WY (2008) Preparations and characterization of novel photocatalysts with mesoporous titanium dioxide (TiO2) via a sol–gel method. Mater Chem Phys 109(2-3):275–280. CrossRefGoogle Scholar
  25. 25.
    Xie Y, Wu Z, Wu Q, Liu M, Piao L (2014) Effect of different base structures on the performance of the hierarchical TiO2 photocatalysts. Catal Today 225:74–79. CrossRefGoogle Scholar
  26. 26.
    Lee HU, Lee SC, Cho SH, Son B, Lee SJ, Kim HJ, Lee J (2013) Highly visible-light active nanoporous TiO2 photocatalysts for efficient solar photocatalytic applications. Appl Catal B Environ 129:106–113. CrossRefGoogle Scholar
  27. 27.
    Zhang L, Xu L, Wang J, Cai J, Xu J, Zhou H, Zhong Y, Chen D, Zhang J, Cao CN (2012) Enhanced energy storage of a UV-irradiated three-dimensional nanostructured TiO2–Ni(OH)2 composite film and its electrochemical discharge in the dark. J Electroanal Chem 683:55–61. CrossRefGoogle Scholar
  28. 28.
    Rai AK, Anh LT, Gim J, Mathew V, Kang J, Paul BJ, Song J, Kim J (2013) Simple synthesis and particle size effects of TiO2 nanoparticle anodes for rechargeable lithium ion batteries. Electrochim Acta 90:112–118. CrossRefGoogle Scholar
  29. 29.
    Yang X, Teng D, Liu B, Yu Y, Yang X (2011) Nanosized anatase titanium dioxide loaded porous carbon nanofiber webs as anode materials for lithium-ion batteries. Electrochem Commun 13(10):1098–1101. CrossRefGoogle Scholar
  30. 30.
    Oh SW, Park SH, Sun YK (2006) Hydrothermal synthesis of nano-sized anatase TiO2 powders for lithium secondary anode materials. J Power Sources 161(2):1314–1318. CrossRefGoogle Scholar
  31. 31.
    Subramanian V, Karki A, Gnanasekar KI, Eddy FP, Rambabu B (2006) Nanocrystalline TiO2 (anatase) for Li-ion batteries. J Power Sources 159(1):186–192. CrossRefGoogle Scholar
  32. 32.
    Liu G, Qu J, Wang H (2013) Morphology-control synthesis and electrochemical performance of titanate and anatase TiO2. J Alloys Compd 578:345–348. CrossRefGoogle Scholar
  33. 33.
    Choi MG, Lee YG, Song SW, Kim KM (2010) Lithium-ion battery anode properties of TiO2 nanotubes prepared by the hydrothermal synthesis of mixed (anatase and rutile) particles. Electrochim Acta 55(20):5975–5983. CrossRefGoogle Scholar
  34. 34.
    Lin KS, Cheng HW, Chen WR, Wu JF (2010) Synthesis, characterization and application of anatase-typed titania nanoparticles. J Environ Eng Manag 20:69–76Google Scholar
  35. 35.
    Deedar N, Irfan A, Ishtiaq Q (2009) Evaluation of the adsorption potential of titanium dioxide nanoparticles for arsenic removal. J Environ Sci 21:402–408CrossRefGoogle Scholar
  36. 36.
    Li Z, Hong L, Guo B (2005) Physicochemical and electrochemical characterization of anatase titanium dioxide nanoparticles. J Power Sources 143(1-2):231–235. CrossRefGoogle Scholar
  37. 37.
    Kun G (2007) Strongly intrinsic anharmonicity in the low-frequency Raman mode in nanocrystalline anatase TiO2. Physica B 398:33–37CrossRefGoogle Scholar
  38. 38.
    Orendorz A, Brodyanski A, Losch J, Bai LH, Chen ZH, Le YK, Ziegler C, Gnaser H (2007) Phase transformation and particle growth in nanocrystalline anatase TiO2 films analyzed by X-ray diffraction and Raman spectroscopy. Surf Sci 601(18):4390–4394. CrossRefGoogle Scholar
  39. 39.
    Cheng G, Akhtar MS, Yang O-B, Stadler FJ (2013) Structure modification of anatase TiO2 nanomaterials-based photoanodes for efficient dye-sensitized solar cells. Electrochim Acta 113:527–535. CrossRefGoogle Scholar
  40. 40.
    Exnar I, Kavan L, Huang SY, Gratzel M (1997) Novel 2 V rocking-chair lithium battery based on nano-crystalline titanium dioxide. J Power Sources 68(2):720–722. CrossRefGoogle Scholar
  41. 41.
    Kavan L, Tathousky J, Gratzel M, Shklover V, Zukal A (2000) Surfactant-templated TiO2 (anatase), characteristic features of lithium insertion electrochemistry in organized nanostructures. J Phys Chem B 104(50):12012–12020. CrossRefGoogle Scholar
  42. 42.
    Cava RJ, Murphy DW, Zahurak S, Santoro A, Roth RS (1984) The crystal structures of the lithium-inserted metal oxides Li0.5TiO2 anatase, LiTi2O4. J Solid State Chem 53(1):64–75. CrossRefGoogle Scholar
  43. 43.
    Yang Z, Choi D, Kerisit S, Rosso KM, Wang D, Zhang J, Graff G, Liu J (2009) Nanostructures and lithium electrochemical reactivity of lithium titanites and tinanium oxides. J Power Sources 192(2):588–598. CrossRefGoogle Scholar
  44. 44.
    Kim J, Cho J (2007) Rate characteristics of anatase TiO2 nanotubes and nanorods for lithium battery anode materials at room temperature. J Electrochem Soc 154(6):A542–A546. CrossRefGoogle Scholar
  45. 45.
    Luttrell T, Halpegamage S, Tao J, Kramer A, Sutter E, Batzill M (2014) Why is anatase a better photocatalyst than rutile? Model studies on epitaxial TiO2 films. Sci Rep 4:4043CrossRefGoogle Scholar
  46. 46.
    Brinker CJ, Hurd AJ, Schunk PR, Frye GC, Ashley CS (1992) Review of sol-gel thin film formation. J Non-Cryst Solids 147-148:424–436. CrossRefGoogle Scholar
  47. 47.
    Tan L, Cao C, Yang H, Wang B, Li L (2013) Nitrogen-doped carbon coated TiO2 anode material for lithium-ion batteries. Mater Lett 109:195–198. CrossRefGoogle Scholar
  48. 48.
    Levi MD, Salitra G, Markovsky B, Teller H, Aurbach D, Heider U, Heider L (1999) Solid-state electrochemical kinetics of Li-ion intercalation into Li1-xCoO2: simultaneous application of electroanalytical techniques SSCV, PITT, and EIS. J Electrochem Soc 146(4):1279–1289. CrossRefGoogle Scholar
  49. 49.
    Kanamura K, Yuasa K, Takehara Z (1987) Diffusion of lithium in the TiO2 cathode of a lithium battery. J Power Sources 20(1-2):127–134. CrossRefGoogle Scholar
  50. 50.
    Cantao MP, Cisneros JI, Torresi RM (1994) Kinetic study of lithium electroinsertion in titanium oxide thin films. J Phys Chem 98(18):4865–4869. CrossRefGoogle Scholar
  51. 51.
    Lindstrom H, Sodergren S, Solbrand A, Rensmo H, Hjelm J, Hagfeldt A, Lindquist S (1997) Li+ ion insertion in TiO2 (anatase). 2. Voltammetry on nanoporous films. J Phys Chem B 101(39):7717–7722. CrossRefGoogle Scholar
  52. 52.
    Lindstrom H, Sodergren S, Solbrand A, Rensmo H, Hjelm J, Hagfeldt A, Lindquist S (1997) Li+ ion insertion in TiO2 (anatase). 1. Chronoamperometry on CVD films and nanoporous films. J Phys Chem B 101(39):7710–7716. CrossRefGoogle Scholar
  53. 53.
    Kavan L, Grätzel M, Gilbert SE, Klemenz C, Scheel HJ (1996) Electrochemical and photoelectrochemical investigation of single-crystal anatase. J Am Chem Soc 118(28):6716–6723. CrossRefGoogle Scholar
  54. 54.
    Wagemaker M, Van de Krol R, Kentgens APM, van Well AA, Mulder FM (2001) Two phase morphology limits lithium diffusion in TiO2 (anatase): a 7Li MAS NMR study. J Am Chem Soc 123(46):11454–11461. CrossRefPubMedGoogle Scholar
  55. 55.
    Dylla AG, Lee JA, Stevenson KJ (2012) Influence of mesoporosity on lithium-ion storage capacity and rate performance of nanostructured TiO2(B). Langmuir 28(2012):2897–2903. CrossRefPubMedGoogle Scholar
  56. 56.
    Zec N, Cvjeticanin N, Bester-Rogac M, Vranes M, Gadzuric S (2017) Electrochemical performance of anatase TiO2 nanotube arrays electrode in ionic liquid based electrolyte for lithium ion batteries. J Electrochem Soc 164(8):H5100–H5107. CrossRefGoogle Scholar
  57. 57.
    Tan L, Pan L, Cao C, Wang B, Li L (2014) Nitrogen-doped carbon coated TiO2 nanocomposites as anode material to improve cycle life for lithium-ion batteries. J Power Sources 253:193–200. CrossRefGoogle Scholar
  58. 58.
    Liu Y, Yang Y (2016) Recent progress of TiO2-based anodes for Li ion batteries, J. Nano 2016:8123652Google Scholar
  59. 59.
    Fu Y, Ming H, Zhou Q, Jin L, Li X, Zheng J (2014) Nitrogen-doped carbon coating inside porous TiO2 using small nitrogen-containing molecules for improving performance of lithium-ion batteries. Electrochim Acta 134:478–485. CrossRefGoogle Scholar
  60. 60.
    Li S, Ge P, Zhang C, Sun W, Hou H, Ji X (2017) The electrochemical exploration of double carbon-wrapped Na3V2(PO4)3: towards long-time cycling and superior rate sodium-ion battery cathode. J Power Sources 366:249–258. CrossRefGoogle Scholar
  61. 61.
    Ge P, Cao X, Hou H, Li S, Ji X (2017) Rod like Sb2Se3 wrapped with carbon: the exploring of electrochemical properties in sodium-ion batteries. ACS Appl Mater Interfaces 9(40):34979–34989. CrossRefPubMedGoogle Scholar
  62. 62.
    Ge P, Hou H, Ji X, Huang Z, Li S, Huang L (2018) Enhanced stability of sodium storage exhibited by carbon coated Sb2S3 hollow spheres. Mater Chem Phys 203:185–192. CrossRefGoogle Scholar
  63. 63.
    Zhou W, Sun F, Pan K, Tian G, Jiang B, Ren Z, Tian C, Fu H (2011) Well-ordered large-pore mesoporous anatase TiO2 with remarkably high thermal stability and improved crystallinity: preparation, characterization, and photocatalytic performance. Adv Func Mater 21(2011):1922–1930. CrossRefGoogle Scholar
  64. 64.
    Bai X, Li T, Qi YX, Wang YX, Yin LW, Li H, Lun N, Bai YJ (2016) One-step fabricating nitrogen-doped TiO2 nanoparticles coated with carbon to achieve excellent high-rate lithium storage performance. Electrochim Acta 187:389–396. CrossRefGoogle Scholar
  65. 65.
    Bresser D, Kim G-T, Binetti E, Striccoli M, Comparelli R, Seidel S, Ozkaya D, Copley M, Bishop P, Paillard E, Passerini S (2015) Transforming anatase TiO2 nanorods into ultrafine nanoparticles for advanced electrochemical performance. J Power Sources 294:406–413. CrossRefGoogle Scholar
  66. 66.
    Patra S, Davoisne C, Bouyanfif H, Foix D, Sauvage F (2015) Phase stability frustration on ultra-nanosized anatase TiO2. Sci Rep 5(1):10928. CrossRefPubMedPubMedCentralGoogle Scholar
  67. 67.
    Patra S, Davoisne C, Bruyre S, Bouyanfif H, Cassaignon S, Taberna P-L, Sauvage F (2013) Room-temperature synthesis of high surface area anatase TiO2 exhibiting a complete lithium insertion solid solution. Part Part Syst Charact 30(12):1093–1104. CrossRefGoogle Scholar
  68. 68.
    Zaghib K, Mauger A, Gendron F, Julien CM (2008) Surface effects on the physical and electrochemical properties of thin LiFePO4 particles. Chem Mater 20(2):462–469. CrossRefGoogle Scholar
  69. 69.
    Zaghib K, Charest P, Dontigny M, Guerfi A, Lagac M, Mauger A, Kopec M, Julien CM (2010) LiFePO4: from molten ingot to nanoparticles with high-rate performance in Li-ion batteries. J Power Sources 195(24):8280–8288. CrossRefGoogle Scholar
  70. 70.
    Trudeau ML, Laul D, Veillette R, Serventi AM, Mauger A, Julien CM, Zaghib K (2011) In situ high-resolution transmission electron microscopy synthesis observation of nanostructured carbon coated LiFePO4. J Power Sources 196:7386–7394CrossRefGoogle Scholar
  71. 71.
    Guo BJ, Yu K, Fu H, Hua QQ, Qi RJ, Li HL, Song HL, Guo S, Zhu ZQ (2015) Firework-shaped TiO2 microspheres embedded with few-layer MoS2 as an anode material for excellent performance lithium-ion batteries. J Mater Chem A 3(12):6392–6401. CrossRefGoogle Scholar
  72. 72.
    Yu XY, Wu HB, Yu L, Ma FX, Lou XW (2015) Rutile TiO2 submicroboxes with superior lithium storage properties. Angew Chem 54(13):4001–4004. CrossRefGoogle Scholar
  73. 73.
    Tian Q, Zhang Z, Yang L, Hirano SI (2015) Morphology-engineered and TiO2(B)-introduced anatase TiO2 as an advanced anode material for lithium-ion batteries. J Mater Chem A 3(28):14721–14730. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • S. S. El-Deen
    • 1
  • A. M. Hashem
    • 2
    • 3
  • A. E. Abdel Ghany
    • 2
    • 4
  • S. Indris
    • 3
  • H. Ehrenberg
    • 3
  • A. Mauger
    • 4
  • C. M. Julien
    • 4
    Email author
  1. 1.Department of Nuclear Chemistry, Hot Laboratories CenterAtomic Energy AuthorityInshasEgypt
  2. 2.Inorganic Chemistry DepartmentNational Research CentreGizaEgypt
  3. 3.Karlsruhe Institute of Technology (KIT)Institute for Applied Materials-Energy Storage Systems (IAM-ESS)Eggenstein-LeopoldshafenGermany
  4. 4.Institut de Minéralogie, de Physique des Matériaux et de Cosmologie (IMPMC)Sorbonne UniversitéParisFrance

Personalised recommendations