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SnO2 nano-particles imbedded in graphene bulk as anode material for lithium-ion batteries

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Abstract

SnO2 is recently considered as one of the most promising candidates for anode material of lithium-ion batteries(LIBs). However, its poor electronic conductivity and serious volume effect limit its application. Here, SnO2 nano-particles are imbedded in porous graphene bulk through destabilized solvothermal reaction. High weight loading of SnO2 (91.5 wt%) and larger surface area of 202.1 m2 g−1 are obtained to ensure high specific capacities. Thus, high reversible discharge/charge capacities of 1361/1341 mAh g−1 remained after 100 cycles at 0.2 A g−1. Even at 2.0 A g−1, SnO2/graphene still delivers high reversible discharge/charge capacities of 1010/1002 mAh g−1 with a capacity retention of 91% after 300 cycles. Such excellent property is ascribed to special hierarchical structure, which not only offers a rapid electron transfer meshwork but also plays as an efficient buffer to release the serious inner stress from the volumetric effect.

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References

  1. Shi SJ, Wang T, Cao M, Wang J, Zhao M, Yang G (2016) Rapid self-assembly spherical Li1.2Mn0.56Ni0.16Co0.08O2 with improved performances by microwave hydrothermal method as cathode for lithium-ion batteries. ACS Appl Mater Interfaces 8:11476–11487

    CAS  PubMed  Google Scholar 

  2. Shi SJ, Zhang S, Wu Z, Wang T, Zong J, Zhao M, Yang G (2017) Full microwave synthesis of advanced Li-rich manganese based cathode material for lithium ion batteries. J Power Sources 337:82–91

    CAS  Google Scholar 

  3. Tarascon JM, Armand M (2001) Issues and challenges facing rechargeable lithium batteries. Nature 414:359–367

    CAS  PubMed  Google Scholar 

  4. Li Z, Lv W, Zhang C, Qin J, Wei W, Shao J-J, Wang D-W, Li B, Kang F, Yang Q-H (2014) Nanospace-confined formation of flattened Sn sheets in pre-seeded graphenes for lithium ion batteries. Nanoscale 6:9554–9558

    CAS  PubMed  Google Scholar 

  5. Goodenough JB (2015) Energy storage materials: a perspective. Energy Storage Mater 1:158–161

    Google Scholar 

  6. Xia X, Deng S, Xie D, Wang Y, Feng S, Wu J, Tu J (2018) Boosting sodium ion storage by anchoring MoO2 on vertical graphene arrays. J Mater Chem A 6:15546–15552

    CAS  Google Scholar 

  7. Yao Z, Xia X, Xie D, Wang Y, Zhou C-A, Liu S, Deng S, Wang X, Tu J (2018) Enhancing ultrafast lithium ion storage of Li4Ti5O12 by tailored TiC/C core/shell skeleton plus nitrogen doping. Adv Funct Mater 28:1802756

    Google Scholar 

  8. Xia X, Deng S, Feng S, Wu J, Tu J (2017) Hierarchical porous Ti2Nb10O29 nanospheres as superior anode materials for lithium ion storage. J Mater Chem A 5:21134–21139

    CAS  Google Scholar 

  9. Zhong Y, Xia X, Deng S, Xie D, Shen S, Zhang K, Guo W, Wang X, Tu J (2018) Spore carbon from Aspergillus oryzae for advanced electrochemical energy storage. Adv Mater 30:1805165

    Google Scholar 

  10. Wu H, Zheng G, Liu N, Carney TJ, Yang Y, Cui Y (2012) Engineering empty space between Si nanoparticles for lithium-ion battery anodes. Nano Lett 12:904–909

    CAS  PubMed  Google Scholar 

  11. Lee B-S, Son S-B, Park K-M, Seo J-H, Lee S-H, Choi I-S, Oh K-H, Yu W-R (2012) Fabrication of Si core/C shell nanofibers and their electrochemical performances as a lithium-ion battery anode. J Power Sources 206:267–273

    CAS  Google Scholar 

  12. Su H, Xu Y-F, Feng S-C, Wu Z-G, Sun X-P, Shen C-H, Wang J-Q, Li J-T, Huang L, Sun S-G (2015) Hierarchical Mn2O3 hollow microspheres as anode material of lithium ion battery and its conversion reaction mechanism investigated by XANES. ACS Appl Mater Interfaces 7:8488–8494

    CAS  PubMed  Google Scholar 

  13. Qiu Y, Xu G-L, Yan K, Sun H, Xiao J, Yang S, Sun S-G, Jin L, Deng H (2011) Morphology-conserved transformation: synthesis of hierarchical mesoporous nanostructures of Mn2O3 and the nanostructural effects on Li-ion insertion/deinsertion properties. J Mater Chem 21:6346–6353

    CAS  Google Scholar 

  14. Li K, Shua F, Guo X, Xue D (2015) Surfactant-assisted crystallization of porous Mn2O3 anode materials for Li-ion batteries. CrystEngComm 17:5094–5100

    CAS  Google Scholar 

  15. Liu L, Guo Y, Wang Y, Yang X, Wang S, Guo H (2013) Hollow NiO nanotubes synthesized by bio-templates as the high performance anode materials of lithium-ion batteries. Electrochim Acta 114:42–47

    CAS  Google Scholar 

  16. Li Q, Chen Y, Yang T, Lei D, Zhang G, Mei L, Chen L, Li Q, Wang T (2013) Preparation of 3D flower-like NiO hierarchical architectures and their electrochemical properties in lithium-ion batteries. Electrochim Acta 90:80–89

    CAS  Google Scholar 

  17. Bell J, Ye R, Ahmed K, Liu C, Ozkan M, Ozkan CS (2015) Free-standing Ni–NiO nanofiber cloth anode for high capacity and high rate Li-ion batteries. Nano Energy 18:47–56

    CAS  Google Scholar 

  18. Zheng F, Zhu D, Chen Q (2014) Facile fabrication of porous NixCo3–xO4 nanosheets with enhanced electrochemical performance as anode materials for Li-ion batteries. ACS Appl Mater Interfaces 6:9256–9264

    CAS  PubMed  Google Scholar 

  19. Zhang M, Sun Z, Zhang T, Sui D, Ma Y, Chen Y (2016) Excellent cycling stability with high SnO2 loading on a three-dimensional graphene network for lithium ion batteries. Carbon 102:32–38

    CAS  Google Scholar 

  20. Dai R, Sun W, Wang Y (2016) Ultrasmall tin nanodots embedded in nitrogen-doped mesoporous carbon: metal-organic-framework derivation and electrochemical application as highly stable anode for Lithium ion batteries. Electrochim Acta 217:123–131

    CAS  Google Scholar 

  21. Dirican M, Yanilmaz M, Fu K, Lu Y, Kizil H, Zhang X (2014) Carbon-enhanced electrodeposited SnO2/carbon nanofiber composites as anode for lithium-ion batteries. J Power Sources 264:240–247

    CAS  Google Scholar 

  22. Liu Z, Song T, Kim JH, Li Z, Xiang J, Lu T, Paik U (2016) Partially reduced SnO2 nanoparticles anchored on carbon nanofibers for high performance sodium-ion batteries. Electrochem Commun 72:91–95

    CAS  Google Scholar 

  23. Deng Y, Fang C, Chen G (2016) The developments of SnO2/graphene nanocomposites as anode materials for high performance lithium ion batteries: a review. J Power Sources 304:81–101

    CAS  Google Scholar 

  24. Zhang C, Peng X, Guo Z, Cai C, Chen Z, Wexler D, Li S, Liu H (2012) Carbon-coated SnO2/graphene nanosheets as highly reversible anode materials for lithium ion batteries. Carbon 50:1897–1903

    CAS  Google Scholar 

  25. Zheng Y, Zhou T, Zhang C, Mao J, Liu H, Guo Z (2016) Boosted charge transfer in SnS/SnO2 heterostructures: toward high rate capability for sodium-ion batteries. Angew Chem Int Ed 55:3408–3413

    CAS  Google Scholar 

  26. Courtney IA, Dahn JR (1997) Electrochemical and in situ X-ray diffraction studies of the reaction of Lithium with tin oxide composites. J Electrochem Soc 144:2045–2052

    CAS  Google Scholar 

  27. Cho JS, Kang YC (2015) Nanofibers comprising yolk–shell Sn@void@SnO/SnO2 and hollow SnO/SnO2 and SnO2 nanospheres via the Kirkendall diffusion effect and their electrochemical properties. Small 11:4673–4681

    CAS  PubMed  Google Scholar 

  28. Zhou X, Wan LJ, Guo YG (2013) Binding SnO2 nanocrystals in nitrogen-doped graphene sheets as anode materials for lithium-ion batteries. Adv Mater 25:2152–2157

    CAS  PubMed  Google Scholar 

  29. Wu C, Maier J, Yu Y (2015) Sn-based nanoparticles encapsulated in a porous 3D graphene network: advanced anodes for high-rate and long life Li-ion batteries. Adv Funct Mater 25:3488–3496

    CAS  Google Scholar 

  30. Wang X, Cao X, Bourgeois L, Guan H, Chen S, Zhong Y, Tang DM, Li H, Zhai T, Li L, Bando Y, Golberg D (2012) N-doped graphene-SnO2 sandwich paper for high-performance lithium-ion batteries. Adv Funct Mater 22:2682–2690

    CAS  Google Scholar 

  31. Huang JY, Zhong L, Wang CM, Sullivan JP, Xu W, Zhang LQ, Mao SX, Hudak NS, Liu XH, Subramanian A, Fan H, Qi L, Kushima A, Li J (2010) In situ observation of the electrochemical lithiation of a single SnO2 nanowire electrode. Science 330:1515–1520

    CAS  PubMed  Google Scholar 

  32. Kim H, Park GO, Kim Y, Muhammad S, Yoo J, Balasubramanian M, Cho Y-H, Kim M-G, Lee B, Kang K, Kim H, Kim JM, Yoon W-S (2014) New insight into the reaction mechanism for exceptional capacity of ordered mesoporous SnO2 electrodes via synchrotron-based X-ray analysis. Chem Mater 26:6361–6370

    CAS  Google Scholar 

  33. Kim C, Noh M, Choi M, Cho J, Park B (2005) Critical size of a nano SnO2 electrode for Li-secondary battery. Chem Mater 17:3297–3301

    CAS  Google Scholar 

  34. Liang J, Yu XY, Zhou H, Wu HB, Ding S, Lou XW (2014) Bowl-like SnO2@carbon hollow particles as an advanced anode material for lithium-ion batteries. Angew Chem Int Ed 53:12803–12807

    CAS  Google Scholar 

  35. Brousse T, Retoux R, Herterich U, Schleich DM (1998) Thin-film crystalline SnO2-lithium electrodes. J Electrochem Soc 145:1–4

    CAS  Google Scholar 

  36. Paek S-M, Yoo E, Honma I (2009) Enhanced cyclic performance and lithium storage capacity of SnO2/graphene nanoporous electrodes with three-dimensionally delaminated flexible structure. Nano Lett 9:72–75

    CAS  PubMed  Google Scholar 

  37. Lou XW, Wang Y, Yuan C, Lee JY, Archer LA (2006) Template-free synthesis of SnO2 hollow nanostructures with high lithium storage capacity. Adv Mater 18:2325–2329

    CAS  Google Scholar 

  38. An K, Lee N, Park J, Kim SC, Hwang Y, Park J-G, Kim J-Y, Park J-H, Han MJ, Yu J, Hyeon T (2006) Synthesis, characterization, and self-assembly of pencil-shaped CoO nanorods. J Am Chem Soc 128:9753–9760

    CAS  PubMed  Google Scholar 

  39. Park MS, Wang GX, Kang YM, Wexler D, Dou SX, Liu HK (2007) Preparation and electrochemical properties of SnO2 nanowires for application in lithium-ion batteries. Angew Chem Int Ed 46:750–753

    CAS  Google Scholar 

  40. Wu Z-S, Zhou G, Yin L-C, Ren W, Li F, Cheng H-M (2012) Graphene/metal oxide composite electrode materials for energy storage. Nano Energy 1:107–131

    CAS  Google Scholar 

  41. Zhou D, Song W-L, Li X, Fan L-Z (2016) Hierarchical porous reduced graphene oxide/SnO2 networks as highly stable anodes for lithium-ion batteries. Electrochim Acta 207:9–15

    CAS  Google Scholar 

  42. Prabakar SJR, Hwang YH, Bae EG, Shim S, Kim D, Lah MS, Sohn KS, Pyo M (2013) SnO2/graphene composites with self-assembled alternating oxide and amine layers for high Li-storage and excellent stability. Adv Mater 25:3307–3312

    CAS  PubMed  Google Scholar 

  43. Chen L, Ma X, Wang M, Chen C, Ge X (2016) Hierarchical porous SnO2/reduced graphene oxide composites for high-performance lithium-ion battery anodes. Electrochim Acta 215:42–49

    CAS  Google Scholar 

  44. Liu L, Huang X, Guo X, Mao S, Chen J (2016) Decorating in situ ultrasmall tin particles on crumpled N-doped graphene for lithium-ion batteries with a long life cycle. J Power Sources 328:482–491

    CAS  Google Scholar 

  45. Yue J, Gu X, Chen L, Wang N, Jiang X, Xu H, Yang J, Qian Y (2014) General synthesis of hollow MnO2, Mn3O4 and MnO nanospheres as superior anode materials for lithium ion batteries. J Mater Chem A 2:17421–17426

    CAS  Google Scholar 

  46. Su L, Zhou Z, Qin X, Tang Q, Wu D, Shen P (2013) CoCO3 submicrocube/graphene composites with high lithium storage capability. Nano Energy 2:276–282

    CAS  Google Scholar 

  47. Shi S, Deng S, Zhang M, Zhao M, Yang G (2017) Rapid microwave synthesis of self-assembled hierarchical Mn2O3 microspheres as advanced anode material for lithium ion batteries. Electrochim Acta 224:285–294

    CAS  Google Scholar 

  48. Wang F, Jiao H, He E, Yang S, Chen Y, Zhao M, Song X (2016) Facile synthesis of ultrafine SnO2 nanoparticles embedded in carbon networks as a high-performance anode for lithium-ion batteries. J Power Sources 326:78–83

    CAS  Google Scholar 

  49. Deng D, Lee JY (2009) Reversible storage of lithium in a rambutan-like tin–carbon electrode. Angew Chem Int Ed 48:1660–1663

    CAS  Google Scholar 

  50. Cheng Y, Huang J, Li J, Xu Z, Cao L, Qi H (2016) Synergistic effect of the core-shell structured Sn/SnO2/C ternary anode system with the improved sodium storage performance. J Power Sources 324:447–454

    CAS  Google Scholar 

  51. Xiao S, Pan D, Wang L, Zhang Z, Lyu Z, Dong W, Chen X, Zhang D, Chen W, Li H (2016) Porous CuO nanotubes/graphene with sandwich architecture as high-performance anodes for lithium-ion batteries. Nanoscale 8:19343–19351

    CAS  PubMed  Google Scholar 

  52. Jadhav HS, Thorat GM, Kale BB, Seo JG (2017) Mesoporous Mn2O3/reduced graphene oxide (rGO) composite with enhanced electrochemical performance for Li-ion battery. Dalton Trans 46:9777–9783

    CAS  PubMed  Google Scholar 

  53. Xu B, Guan X, Zhang LY, Liu X, Jiao Z, Liu X, Hu X, Zhao XS (2018) A simple route to preparing γ-Fe2O3/RGO composite electrode materials for lithium ion batteries. J Mater Chem A 6:4048–4054

    CAS  Google Scholar 

  54. Chen B, Qian H, Xu J, Qin L, Wu Q-H, Zheng M, Dong Q (2014) Study on SnO2/graphene composites with superior electrochemical performance for lithium-ion batteries. J Mater Chem A 2:9345–9352

    CAS  Google Scholar 

  55. Li S, Xie W, Wang S, Jiang X, Peng S, He D (2014) Facile synthesis of rGO/SnO2 composite anodes for lithium ion batteries. J Mater Chem A 2:17139–17145

    CAS  Google Scholar 

  56. Wang T, Shi S, Li Y, Zhao M, Chang X, Wu D, Wang H, Peng L, Wang P, Yang G (2016) Study of microstructure change of carbon nanofibers as binder-free anode for high-performance lithium-ion batteries. ACS Appl Mater Interfaces 8:33091–33101

    CAS  PubMed  Google Scholar 

  57. Jiang Y, Yuan T, Sun W, Yan M (2012) Electrostatic spray deposition of porous SnO2/graphene anode films and their enhanced lithium-storage properties. ACS Appl Mater Interfaces 4:6216–6220

    CAS  PubMed  Google Scholar 

  58. Cong H-P, Xin S, Yu S-H (2015) Flexible nitrogen-doped graphene/SnO2 foams promise kinetically stable lithium storage. Nano Energy 13:482–490

    CAS  Google Scholar 

  59. Ma X-H, Wan Q-Y, Huang X, Ding C-X, Jin Y, Guan Y-B, Chen C-H (2014) Synthesis of three-dimensionally porous MnO thin films for lithium-ion batteries by improved electrostatic spray deposition technique. Electrochim Acta 121:15–20

    CAS  Google Scholar 

  60. Wang R, Xu C, Sun J, Gao L, Yao H (2014) Solvothermal-induced 3D macroscopic SnO2/nitrogen-doped graphene aerogels for high capacity and long-life lithium storage. ACS Appl Mater Interfaces 6:3427–3436

    CAS  PubMed  Google Scholar 

  61. Liu C-L, Wang Y, Zhang C, Li X-S, Dong W-S (2014) In situ synthesis of α-MoO3/graphene composites as anode materials for lithium ion battery. Mater Chem Phys 143:1111–1118

    CAS  Google Scholar 

  62. Lindström H, Södergren S, Solbrand A, Rensmo H, Hjelm J, Hagfeldt A, Lindquist S-E (1997) Li+ ion insertion in TiO2 (anatase). 2. Voltammetry on nano-porous films. J Phys Chem B 101:7717–7722

    Google Scholar 

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Acknowledgements

The authors acknowledge the supports of the National Natural Science Youth Foundation of China (Grant No. 21701017), Natural Science Youth Foundation of Jiangsu Province of China (Grant No. BK20160404), and Qinglan Project of Jiangsu Universities.

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This study was funded by Grant No. 21701017, BK20160404.

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  1. Jiangsu Laboratory of Advanced Functional Material, Changshu Institute of Technology, Changshu, 215500, China

    Xiaoyan Hua, Yuwei Shen & Shaojun Shi

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  1. Xiaoyan Hua
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  2. Yuwei Shen
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Hua, X., Shen, Y. & Shi, S. SnO2 nano-particles imbedded in graphene bulk as anode material for lithium-ion batteries. Ionics 25, 5769–5778 (2019). https://doi.org/10.1007/s11581-019-03131-0

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