High-performance tin-titanium thin-film anodes prepared by magnetron co-sputtering for lithium-ion microbatteries

  • Guoliang Bai
  • Chunhua WangEmail author
  • Ming Luo
  • Junwei WangEmail author
  • Qibo Luo
  • Jiaojiao Luo
  • Benqiu Wang
  • Jie Zhao
Original Paper


A new anode material of Sn-Ti thin film was successfully prepared by magnetron co-sputtering of two separate targets at the atmosphere of Ar at normal temperature. The structure, surface morphology, and electrochemical performance of the Sn-Ti thin film electrodes are examined by X-ray diffraction spectroscopy, scanning electron microscopy, and electrochemical tests. Furthermore, the effects on the electrochemical performance of the Ti content in the Sn-Ti thin films are studied. Results show that increasing the power of Ti target can improve the cyclic performance of Sn-Ti thin film electrodes. It is very interesting that no any cracks or material pulverization are observed on these Sn-Ti thin films, which indicate that the Ti can improve the stability of Sn-based anode materials. Such improved electrochemical properties benefit from the good mechanical support by Ti and uniform Ti doping.


Sn-Ti thin film Anodes Magnetron co-sputtering Lithium-ion microbatteries 


Funding information

This work was supported by the open fund of the Key Laboratory of Optoelectronic and Magnetism Functional Materials of Anhui Province (Grant No. ZD2016005, ZD2017006), the Natural Science Foundation of Anhui Education Department (Grant No. KJ2018A0372, KJ2019A0546), the Youth Project of Natural Science Foundation of Anhui Province (Grant No. 1908085QB61, 1708085MB49), the Key Project of Outstanding Young Scholars in Colleges and Universities of Anhui Province (Grant No. gxyqZD2017062), and the foundation of National Key Laboratory (Grant No. 6142808180205).


  1. 1.
    Souquet JL, Duclot M (2002) Thin film lithium batteries. Solid State Ionics 148(3-4):375–379Google Scholar
  2. 2.
    Dyer CK (1990) A novel thin-film electrochemical device for energy conversionCuO. Nature 343(6258):547–548Google Scholar
  3. 3.
    Chen CH, Buysman AAJ, Kelder EM, Schoonman J (1995) Fabrication of LiCoO2 thin film cathodes for rechargeable lithium battery by electrostatic spray pyrolysis. Solid State Ionics 80(1-2):1–4Google Scholar
  4. 4.
    Zhu X, Guo Z, Du G, Zhang P, Liu H (2010) LiCoO2 cathode thin film fabricated by RF sputtering for lithium ion microbatteries. Surf Coat Technol 204(11):1710–1714Google Scholar
  5. 5.
    Wook JS, Lee SM (2007) LiCoO2 ∕ Ag multilayer film cathodes for thin-film rechargeable lithium batteries. J Electrochem Soc 154(1):A22–A25Google Scholar
  6. 6.
    Kalinauskas P, Norkus E, Mockus Z, Giraitis R, Juškėnas R (2019) Electrochemical and photoelectrochemical characterization of Cu2SnSe3 thin films deposited on Mo/glass substrates. J Electrochem Soc 166(5):H3107–H3111Google Scholar
  7. 7.
    Daramalla V, Venkatesh G, Kishore B, Munichandraiah N, Krupanidhi SB (2018) Electrochemical performance of amorphous titanium niobium oxide thin films for Li-ion thin film batteries. J Electrochem Soc 165(5):A764–A772Google Scholar
  8. 8.
    Su Q, Pan X, Xie E, Wang Y, Qiu J, Liu X (2006) Influence of temperature on the microstructure of V2O5 film prepared by DC magnetron sputtering. Rare Metals 25(6):82–87Google Scholar
  9. 9.
    Wu X, He Z, Ma M, Xiao Z, Xu M (2006) LiMn2O4 thin films derived by rapid thermal annealing and their performance as cathode materials for Li ion battery. Rare Metals 25(6):620–624Google Scholar
  10. 10.
    Lee WH, Son HC, Moon HS, Kim YI, Sung SH, Kim JY, Lee JG, Park JW (2000) Stoichiometry dependence of electrochemical performance of thin-film SnOx microbattery anodes deposited by radio frequency magnetron sputtering. J Power Sources 89(1):102–105Google Scholar
  11. 11.
    Xie H, Kalisvaart WP, Olsen BC, Luber EJ, Mitlin D, Buriak JM (2017) Sn-Bi-Sb alloys as anode materials for sodium ion batteries. J Mater Chem A 5(20):9661–9670Google Scholar
  12. 12.
    Wang ZD, Shan ZQ, Tian JH, Huang WL, Luo DD, Zhu X, Meng SX (2017) Immersion-plated Cu6Sn5/Sn composite film anode for lithium ion battery. J Mater Sci 52(10):6020–6033Google Scholar
  13. 13.
    Chang XH, Liu ZL, Sun BX, Xie ZW, Zheng XY, Zheng J, Li XG (2018) Sn-C binary nanocomposites for lithium ion batteries: Core-shell vs. multilayer structure. Electrochim Acta 267:1–7Google Scholar
  14. 14.
    Tong YF, Xu Z, Liu C, Zhang GA, Wang J, Wu ZG (2014) Magnetic sputtered amorphous Si/C multilayer thin films as anode materials for lithium ion batteries. J Power Sources 247:78–83Google Scholar
  15. 15.
    Inaba M, Uno T, Tasaka A (2005) Irreversible capacity of electrodeposited Sn thin film anode. J Power Sources 146(1-2):473–477Google Scholar
  16. 16.
    Idota Y, Kubota T, Matsufuji A, Maekawa Y, Miyasaka T (1997) Tin-based amorphous oxide: A high-capacity lithium-ion-storage material. Science 276(5317):1395–1397Google Scholar
  17. 17.
    Lee WW, Lee JM (2014) Novel synthesis of high performance anode materials for lithium-ion batteries (LIBs). J Mater Chem A 2(6):1589–1626Google Scholar
  18. 18.
    Wang XL, Han WQ, Chen JJ, Graetz J (2010) Single-crystal intermetallic M-Sn (M = Fe, Cu, Co, Ni) nanospheres as negative electrodes for lithium-ion batteries. ACS Appl Mater Interfaces 2(5):1548–1551Google Scholar
  19. 19.
    Beaulieu LY, Beattie SD, Hatchard TD, Dahn JR (2003) The electrochemical reaction of lithium with tin studied by in situ AFM. J Electrochem Soc 150(4):A419–A424Google Scholar
  20. 20.
    Beaulieu LY, Hatchard TD, Bonakdarpour A, Fleischauer MD, Dahn JR (2003) Reaction of Li with alloy thin films studied by in situ AFM. J Electrochem Soc 150(11):A1457–A1464Google Scholar
  21. 21.
    Mao O, Dunlap RA, Courtney IA, Dahn JR (1998) In situ Mossbauer effect studies of the electrochemical reaction of lithium with mechanically alloyed Sn2Fe. J Electrochem Soc 145(12):4195–4202Google Scholar
  22. 22.
    Winter M, Besenhard JO (1999) Electrochemical lithiation of tin and tin-based intermetallics and composites. Electrochim Acta 45(1-2):31–50Google Scholar
  23. 23.
    Larcher D, Beattie S, Morcrette M, Edstroem K, Jumas JC, Tarascon JM (2007) Recent findings and prospects in the field of pure metals as negative electrodes for Li-ion batteries. J Mater Chem 17(36):3759–3772Google Scholar
  24. 24.
    Zhang LF, Dou P, Wang WJ, Zheng J, Xu XH (2017) Sn-Cu nanotubes enveloped in three-dimensional interconnected polyaniline hydrogel framework as binder-free anode for lithium-ion battery. Appl Surf Sci 423:245–254Google Scholar
  25. 25.
    Shen Z, Hu Y, Chen RZ, He X, Chen YL, Shao HF, Zhang XW, Wu KS (2017) Split Sn-Cu alloys on carbon nanofibers by one-step heat treatment for long-lifespan lithium-ion batteries. Electrochim Acta 225:350–357Google Scholar
  26. 26.
    Sun LN, Cai HH, Zhang W, Ren XZ, Zhang PX, Liu JH (2016) Preparation and electrochemical performance of Cu6Sn5/CNTs anode materials for lithium-ion batteries. Integr Ferroelectr 171(1):193–202Google Scholar
  27. 27.
    Wu XM, Zhang SC, Qi T, Fang H, Liu GR, Xing YL (2016) Novel insight toward engineering of arrayed Cu@Sn nanoelectrodes: Rational microstructure refinement and its remarkable "harvesting effect" on lithium storage capability. J Power Sources 307:753–761Google Scholar
  28. 28.
    Dong X, Liu WB, Chen X, Yan JZ, Li N, Shi SQ, Zhang SC, Yang XS (2018) Novel three dimensional hierarchical porous Sn-Ni alloys as anode for lithium ion batteries with long cycle life by pulse electrodeposition. Chem Eng J 350:791–798Google Scholar
  29. 29.
    Dou P, Cao ZZ, Zheng J, Wang C, Xu XH (2016) Solid polymer electrolyte coating three-dimensional Sn/Ni bimetallic nanotube arrays for high performance lithium-ion battery anodes. J Alloys Compd 685:690–698Google Scholar
  30. 30.
    Yamamoto T, Nohira T, Hagiwara R, Fukunaga A, Sakai S, Nitta K (2016) Charge-discharge behavior of Sn-Ni alloy film electrodes in an intermediate temperature ionic liquid for the electrolyte of a sodium secondary battery. Electrochim Acta 193:275–283Google Scholar
  31. 31.
    Wan H, Chen ZW, Yuan MQ, Wang JM, Zhang JQ (2015) Highly ordered nanoporous Sn-Ni alloy film anode with excellent lithium storage performance. Mater Lett 138:139–142Google Scholar
  32. 32.
    Li P, Chen Y, Zeng DQ, Xiao QZ, Li ZH, Lei GT (2014) Performance improvement of Sn-Co alloy film anodes for lithium-ion batteries. Funct Mater Lett.
  33. 33.
    Tan CH, Qi GW, Li YP, Guo J, Wang X, Kong DL, Wang HJ, Zhang SY (2013) Performance enhancement of Sn-Co alloys for lithium-ion battery by electrochemical dissolution treatment. J Alloys Compd 574:206–211Google Scholar
  34. 34.
    Ying HJ, Han WQ (2017) Metallic Sn-based anode materials: Application in high-performance lithium-ion and sodium-ion batteries. Adv Sci.
  35. 35.
    Gul H, Uysal M, Cetinkaya T, Guler MO, Alp A, Akbulut H (2014) Preparation of Sn-Co alloy electrode for lithium ion batteries by pulse electrodeposition. Int J Hydrogen Energ 39:21414–21419Google Scholar
  36. 36.
    Jiang AN, Fan X, Zhu J, Ma DQ, Xu XH (2015) Hollow structured Sn-Co nanospheres by galvanic replacement reaction as high-performance anode for lithium ion batteries. Ionics 21(8):2137–2147Google Scholar
  37. 37.
    Das S, Row TNG, Bhattacharyya AJ (2017) Probing the critical role of Sn content in SnSb@C nanofiber anode on Li storage mechanism and battery performance. ACS Omega 2(12):9250–9260Google Scholar
  38. 38.
    Nithyadharseni P, Reddy MV, Nalini B, Ravindran TR, Pillai BC, Kalpana M, Chowdari BVR (2015) Electrochemical studies of CNT/Si-SnSb nanoparticles for lithium ion batteries. Mater Res Bull 70:478–485Google Scholar
  39. 39.
    Yi Z, Han QG, Geng D, Wu YM, Cheng Y, Wang LM (2017) One-pot chemical route for morphology-controllable fabrication of Sn-Sb micro/nano-structures: Advanced anode materials for lithium and sodium storage. J Power Sources 342:861–871Google Scholar
  40. 40.
    Nithyadharseni P, Nalini B, Saravanan P (2014) Electrical and magnetic effect of transition metals in SnSb nanoalloy. Appl Surf Sci 311:503–507Google Scholar
  41. 41.
    Chamas M, Mahmoud A, Tang JL, Sougrati MT, Panero S, Lippens PE (2017) Aging processes in lithiated FeSn2 based negative electrode for Li-ion batteries: A new challenge for tin based intermetallic materials. J Phys Chem C 121:217–224Google Scholar
  42. 42.
    Shi HX, Fang ZW, Zhang X, Li F, Tang YW, Zhou YM, Wu P, Yu GH (2018) Double-network nanostructured hydrogel-derived ultrafine Sn-Fe alloy in three-dimensional carbon framework for enhanced lithium storage. Nano Lett 18(5):3193–3198Google Scholar
  43. 43.
    Shi HX, Zhang AP, Zhang XK, Yin HM, Wang SQ, Tang YW, Zhou YM, Wu P (2018) Pyrolysis of cyano-bridged hetero-metallic aerogels: a general route to immobilize Sn-M (M = Fe, Ni) alloys within a carbon matrix for stable and fast lithium storage. Nanoscale 10(10):4962–4968Google Scholar
  44. 44.
    Liu H, Bi Z, Sun XG, Unocic RR, Paranthaman MP, Dai S, Brown GM (2011) Mesoporous TiO2–B microspheres with superior rate performance for lithium ion batteries. Adv Mater 23(30):3450–3454Google Scholar
  45. 45.
    Li W, Wang F, Feng S, Wang J, Sun Z, Li B, Li Y, Yang J, Elzatahry AA, Xia Y, Zhao D (2013) Sol–gel design strategy for ultradispersed TiO2 nanoparticles on graphene for high-performance lithium Iion batteries. J Am Chem Soc 135(49):18300–18303Google Scholar
  46. 46.
    Wang H, Xi L, Tucek J, Ma C, Yang G, Leung MKH, Zboril R, Niu C, Rogach AL (2014) Synthesis and characterization of tin titanate nanotubes: precursors for nanoparticulate Sn-doped TiO2 anodes with synergistically improved electrochemical performance. ChemElectroChem 1:1563–1569Google Scholar
  47. 47.
    Chen JS, Lou XW (2013) SnO2-based nanomaterials: Synthesis and application in lithium-ion batteries. Small 9(11):1877–1893Google Scholar
  48. 48.
    Ji G, Ding B, Ma Y, Lee JY (2013) Nanostructured SnO2@TiO2 core-shell composites: A high-rate Li-ion anode material usable without conductive additives. Energy Technol 1(10):567–572Google Scholar
  49. 49.
    Tian Q, Mao Y, Zhang X, Yang L (2018) Heterogeneous nanocrystals assembled TiO2/SnO2/C composite for improved lithium storage. Appl Surf Sci 447:408–415Google Scholar
  50. 50.
    Sumiya K, Suzuki J, Takasu R, Sekine K, Takamura T (1999) Enhancement of the electrochemical Li doping/undoping reaction rate of a graphitic material by an evaporated film of Sn, Zn or Pb. J Electroanal Chem 462(2):150–156Google Scholar
  51. 51.
    Li Y, Matsuura R, Saka M (2017) Controlling surface morphology of Sn thin-film to enhance cycling performance in lithium ion batteries. Mater Res Bull 87:155–160Google Scholar
  52. 52.
    Zhang T, Fu LJ, Gao J, Wu YP, Holze R, Wu HQ (2007) Nanosized tin anode prepared by laser-induced vapor deposition for lithium ion battery. J Power Sources 174(2):770–773Google Scholar
  53. 53.
    Liu Y, Wang L, Jiang K, Yang S (2019) Electro-deposition preparation of self-standing Cu-Sn alloy anode electrode for lithium ion battery. J Alloys Compd 775:818–825Google Scholar
  54. 54.
    Kyeremateng NA, Hornebecq V, Knauth P, Djenizian T (2012) Properties of Sn-doped TiO2 nanotubes fabricated by anodization of co-sputtered Ti–Sn thin films. Electrochim Acta 62:192–198Google Scholar
  55. 55.
    Jung YC, Lee SM, Choi JH, Jang SS, Kim DW (2015) All solid-state lithium batteries assembled with hybrid solid electrolytes. J Electrochem Soc 162(4):A704–A710Google Scholar
  56. 56.
    Wang CH, Yang YF, Liu XJ, Zhong H, Xu H, Xu ZB, Shao HX, Ding F (2017) Suppression of lithium dendrite formation by using LAGP-PEO (LiTFSI) composite solid electrolyte and lithium metal anode modified by PEO (LiTFSI) in all-solid-state lithium batteries. ACS Appl Mater Interfaces 9(15):13694–13702Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Anhui Province Key Laboratory of Optoelectronic and Magnetism Functional Materials, Key Laboratory of Functional Coordination Compounds of Anhui Higher Education InstitutesAnqing Normal UniversityAnqingPeople’s Republic of China

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