Journal of Materials Science

, Volume 54, Issue 7, pp 5641–5657 | Cite as

Heteroatom-doped hierarchically porous carbons derived from cucumber stem as high-performance anodes for sodium-ion batteries

  • Chengjie LiEmail author
  • Jianye Li
  • Yingchao ZhangEmail author
  • Xin Cui
  • Haibo Lei
  • Guofu Li
Energy materials


Sodium-ion batteries (SIBs) are regarded as one of the most promising alternatives to lithium-ion batteries (LIBs) for large-scale energy stationary applications due to the abundant reserve of sodium. However, it is still challenging to develop low-cost and high-performance anode materials for SIBs. Herein, heteroatom-doped hard carbons with hierarchically porous and disordered structures are prepared via pyrolysis of natural biomass cucumber stem. The electrochemical performances of the biomass carbon are significantly influenced by the carbonization temperatures due to the different microstructures and heteroatomic contents. The biomass carbon carbonized at 1000 °C delivers the highest reversible capacity of 337.9 mAh g−1 while used as the anode material for SIBs. Furthermore, the biomass carbon achieves a sheet-like morphology with macroscopically open structure after the hydrothermal activation of KOH. It is worth noting that the activated carbon exhibits a high reversible capacity (458.6 mAh g−1), an excellent rate capability (102.6 mAh g−1 at 10 A g−1) and a cycling stability (198.6 mAh g−1 at 0.2 A g−1 over 500 cycles). The enhanced electrochemical properties of the activated carbon can be attributed to the larger surface area and highly developed nanopores, which could significantly facilitate the transport and storage of sodium ions.



The authors gratefully acknowledge the financial support of this research by Key Research and Development Program of Shandong Province (No. 2018JMRH0302), Science and Technology Development Plan of Weifang (No. 2018GX064), Project of Shandong Province Higher Educational Science and Technology Program (No. 2018LS001) and Doctoral Fund Project of Weifang University of Science and Technology (No. 2017BS07).

Compliance with ethical standards

Conflict of interest

There is no conflict of interest.

Supplementary material

10853_2018_3229_MOESM1_ESM.doc (23.1 mb)
Supplementary material 1 (DOC 23626 kb)


  1. 1.
    Dunn B, Kamath H, Tarascon JM (2011) Electrical energy storage for the grid: a battery of choices. Science 334:928–935CrossRefGoogle Scholar
  2. 2.
    Larcher D, Tarascon JM (2015) Towards greener and more sustainable batteries for electrical energy storage. Nat Chem 7:19–29CrossRefGoogle Scholar
  3. 3.
    Goodenough JB, Park KS (2013) The Li-ion rechargeable battery: a perspective. J Am Chem Soc 135:1167–1176CrossRefGoogle Scholar
  4. 4.
    Scrosati B, Hassoun J, Sun YK (2011) Lithium-ion batteries. A look into the future. Energy Environ Sci 4:3287–3295CrossRefGoogle Scholar
  5. 5.
    Komaba S, Murata W, Ishikawa T et al (2011) Electrochemical Na insertion and solid electrolyte interphase for hard-carbon electrodes and application to Na-ion batteries. Adv Funct Mater 21:3859–3867CrossRefGoogle Scholar
  6. 6.
    Yabuuchi N, Kubota K, Dahbi M, Komaba S (2014) Research development on sodium-ion batteries. Chem Rev 114:11636–11682CrossRefGoogle Scholar
  7. 7.
    Pan HL, Hu YS, Chen LQ (2013) Room-temperature stationary sodium-ion batteries for large-scale electric energy storage. Energy Environ Sci 6:2338–2360CrossRefGoogle Scholar
  8. 8.
    Ren WH, Zhu ZX, An QY, Mai LQ (2017) Emerging prototype sodium-ion full cells with nanostructured electrode materials. Small 13:1604181CrossRefGoogle Scholar
  9. 9.
    Yuan DD, Liang XM, Wu L, Cao YL, Ai XP, Feng JW, Yang HX (2014) A honeycomb-layered Na3Ni2SbO6: a high-rate and cycle-stable cathode for sodium-ion batteries. Adv Mater 26:6301–6306CrossRefGoogle Scholar
  10. 10.
    Wang YS, Xiao RJ, Hu YS, Avdeev M, Chen LQ (2015) P2-Na0.6[Cr0.6Ti0.4]O2 cation-disordered electrode for high-rate symmetric rechargeable sodium-ion batteries. Nat Commun 6:6954CrossRefGoogle Scholar
  11. 11.
    Xu SY, Wang YS, Ben LB et al (2015) Fe-based tunnel-type Na0.61[Mn0.27Fe0.34Ti0.39]O2 designed by a new strategy as a cathode material for sodium-ion batteries. Adv Energy Mater 5:1501156CrossRefGoogle Scholar
  12. 12.
    Fang YJ, Xiao LF, Ai XP, Cao YL, Yang HX (2015) Hierarchical carbon framework wrapped Na3V2(PO4)3 as a superior high-rate and extended lifespan cathode for sodium-ion batteries. Adv Mater 27:5895–5900CrossRefGoogle Scholar
  13. 13.
    Barpanda P, Oyama G, Nishimura S, Chung SC, Yamada A (2014) A 3.8-V earth-abundant sodium battery electrode. Nat Commun 5:4358CrossRefGoogle Scholar
  14. 14.
    Li C, Miao X, Chu W, Wua P, Tong DG (2015) Hollow amorphous NaFePO4 nanospheres as a high-capacity and high-rate cathode for sodium-ion batteries. J Mater Chem A 3:8265–8271CrossRefGoogle Scholar
  15. 15.
    Qi YR, Mu LQ, Zhao JM, Hu YS, Liu HZ, Dai S (2015) Superior Na-storage performance of low-temperature-synthesized Na3(VO1−xPO4)2F1+2x (0 ≤ x ≤ 1) nanoparticles for Na-ion batteries. Angew Chem 54:9911–9916CrossRefGoogle Scholar
  16. 16.
    Cao YL, Xiao LF, Sushko ML et al (2012) Sodium ion insertion in hollow carbon nanowires for battery applications. Nano Lett 12:3783–3787CrossRefGoogle Scholar
  17. 17.
    Song JX, Yu ZX, Gordin ML, Li XL, Peng HS, Wang DH (2015) Advanced sodium ion battery anode constructed via chemical bonding between phosphorus, carbon nanotube, and cross-linked polymer binder. ACS Nano 9:11933–11941CrossRefGoogle Scholar
  18. 18.
    Wang HG, Wu Z, Meng FL, Ma DL, Huang XL, Wang LM, Zhang XB (2013) Nitrogen-doped porous carbon nanosheets as low-cost, high-performance anode material for sodium-ion batteries. Chemsuschem 6:56–60CrossRefGoogle Scholar
  19. 19.
    Qie L, Chen WM, Wang ZH et al (2012) Nitrogen-doped porous carbon nanofiber webs as anodes for lithium ion batteries with a superhigh capacity and rate capability. Adv Mater 24:2047–2050CrossRefGoogle Scholar
  20. 20.
    Wang XL, Li G, Hassan FM et al (2015) Sulfur covalently bonded graphene with large capacity and high rate for high-performance sodium-ion batteries anodes. Nano Energy 15:746–754CrossRefGoogle Scholar
  21. 21.
    Tang K, Fu LJ, White RJ, Yu LH, Titirici MM, Antonietti M, Maier J (2012) Hollow carbon nanospheres with superior rate capability for sodium-based batteries. Adv Energy Mater 2:873–877CrossRefGoogle Scholar
  22. 22.
    Sun Y, Zhao L, Pan HL et al (2013) Direct atomic-scale confirmation of three-phase storage mechanism in Li4Ti5O12 anodes for room-temperature sodium-ion batteries. Nat Commun 4:1870CrossRefGoogle Scholar
  23. 23.
    Li G, Luo D, Wang XL, Seo MH, Hemmati S, Yu AP, Chen ZW (2017) Enhanced reversible sodium-ion intercalation by synergistic coupling of few-layered MoS2 and S-doped graphene. Adv Funct Mater 27:1702562CrossRefGoogle Scholar
  24. 24.
    Zhu YJ, Wen Y, Fan XL (2015) Red phosphorus-single-walled carbon nanotube composite as a superior anode for sodium ion batteries. ACS Nano 9:3254–3264CrossRefGoogle Scholar
  25. 25.
    Walter M, Doswald S, Kovalenko MV (2016) Inexpensive colloidal SnSb nanoalloys as efficient anode materials for lithium- and sodium-ion batteries. J Mater Chem A 4:7053–7059CrossRefGoogle Scholar
  26. 26.
    Stevens DA, Dahn JR (2000) High capacity anode materials for rechargeable sodium-ion batteries. J Electrochem Soc 147:1271–1273CrossRefGoogle Scholar
  27. 27.
    Xu YX, Lin ZY, Zhong X, Papandrea B, Huang Y, Duan XF (2015) Solvated graphene frameworks as high-performance anodes for lithium-ion batterie. Angew Chem 54:5435–5440CrossRefGoogle Scholar
  28. 28.
    Li W, Zhou M, Li HM, Wang KL, Cheng SJ, Jiang K (2015) A high performance sulfur-doped disordered carbon anode for sodium ion batteries. Energy Environ Sci 8:2916–2921CrossRefGoogle Scholar
  29. 29.
    Qie L, Chen WM, Xiong XQ, Hu CC, Zou F, Hu P, Huang YH (2015) Sulfur-doped carbon with enlarged interlayer distance as a high-performance anode material for sodium-ion batteries. Adv Sci 2:1500195CrossRefGoogle Scholar
  30. 30.
    Xu JT, Wang M, Wickramaratne NP, Jaroniec M, Dou SX, Dai LM (2015) High-performance sodium ion batteries based on a 3D anode from nitrogen-doped graphene foams. Adv Mater 27:2042–2048CrossRefGoogle Scholar
  31. 31.
    Xu DF, Chen CJ, Xie J et al (2016) A hierarchical N/S-codoped carbon anode fabricated facilely from cellulose/polyaniline microspheres for high-performance sodium-ion batteries. Adv Energy Mater 6:1501929CrossRefGoogle Scholar
  32. 32.
    Yang JQ, Zhou XL, Wu DH, Zhao XD, Zhou Z (2017) S-doped N-rich carbon nanosheets with expanded interlayer distance as anode materials for sodium-ion batteries. Adv Mater 29:1604108–1604112CrossRefGoogle Scholar
  33. 33.
    Jo C, Park Y, Jeong J, Lee KT, Lee J (2015) Structural effect on electrochemical performance of ordered porous carbon electrodes for Na-ion batteries. ACS Appl Mater Interfaces 7:11748–11754CrossRefGoogle Scholar
  34. 34.
    Hou HS, Banks CE, Jing MJ, Zhang Y, Ji XB (2016) Carbon quantum dots and their derivative 3D porous carbon frameworks for sodium-ion batteries with ultralong cycle life. Adv Mater 27:7861–7866CrossRefGoogle Scholar
  35. 35.
    Wang L, Yang CL, Dou S et al (2016) Nitrogen-doped hierarchically porous carbon networks: synthesis and applications in lithium-ion battery, sodium-ion battery and zinc-air battery. Electrochim Acta 219:592–603CrossRefGoogle Scholar
  36. 36.
    Zou GQ, Jia XN, Huang ZD et al (2016) Cube-shaped porous carbon derived from MOF-5 as advanced material for sodium-ion batteries. Electrochim Acta 196:413–421CrossRefGoogle Scholar
  37. 37.
    Wang S, Xia L, Yu L, Zhang L, Wang H, Lou XW (2016) Free-standing nitrogen-doped carbon nanofiber films: integrated electrodes for sodium-ion batteries with ultralong cycle life and superior rate capability. Adv Energy Mater 6:1502217–1502223CrossRefGoogle Scholar
  38. 38.
    Hong KL, Qie L, Zeng R et al (2014) Biomass derived hard carbon used as a high performance anode material for sodium ion batteries. J Mater Chem A 2:12733–12738CrossRefGoogle Scholar
  39. 39.
    Liu P, Li YM, Hu YS, Li H, Chen LQ, Huang XJ (2016) A waste biomass derived hard carbon as high-performance anode material for sodium-ion batteries. J Mater Chem A 4:13046–13052CrossRefGoogle Scholar
  40. 40.
    Gaddam RR, Yang DF, Narayan R, Raju KV, Kumar NA, Zhao XS (2016) Biomass derived carbon nanoparticle as anodes for high performance sodium and lithium ion batteries. Nano Energy 26:346–352CrossRefGoogle Scholar
  41. 41.
    Lv WM, Wen FS, Xiang JY et al (2015) Peanut shell derived hard carbon as ultralong cycling anodes for lithium and sodium batteries. Electrochim Acta 176:533–541CrossRefGoogle Scholar
  42. 42.
    Zhang F, Wang KX, Li GD, Chen JS (2009) Hierarchical porous carbon derived from rice straw for lithium ion batteries with high-rate performance. Electrochem Commun 11:130–133CrossRefGoogle Scholar
  43. 43.
    Chen L, Zhang YZ, Lin CH et al (2014) Hierarchically porous nitrogen-rich carbon derived from wheat straw as an ultra-high-rate anode for lithium ion batteries. J Mater Chem A 2:9684–9690CrossRefGoogle Scholar
  44. 44.
    Zhu YY, Chen MM, Li Q, Yuan C, Wang CY (2018) A porous biomass-derived anode for high-performance sodium-ion batteries. Carbon 129:695–701CrossRefGoogle Scholar
  45. 45.
    Lu MJ, Yu WH, Shi J, Liu W, Chen SG, Wang X, Wang HL (2017) Self-doped carbon architectures with heteroatoms containing nitrogen, oxygen and sulfur as high-performance anodes for lithium- and sodium-ion batteries. Electrochim Acta 251:396–406CrossRefGoogle Scholar
  46. 46.
    Hao R, Yang Y, Wang H et al (2018) Direct chitin conversion to N-doped amorphous carbon nanofibers for high-performing full sodium-ion batteries. Nano Energy 45:220–228CrossRefGoogle Scholar
  47. 47.
    Qin DC, Liu ZY, Zhao YZ, Xu GY, Zhang F, Zhang XZ (2018) A sustainable route from corn stalks to N, P-dual doping carbon sheets toward high performance sodium-ion batteries anode. Carbon 130:664–671CrossRefGoogle Scholar
  48. 48.
    Selvamani V, Ravikumar R, Suryanarayanan V, Velayutham D, Gopukumar S (2016) Garlic peel derived high capacity hierarchical N-doped porous carbon anode for sodium/lithium ion cell. Electrochim Acta 190:337–345CrossRefGoogle Scholar
  49. 49.
    Zhang YC, You Y, Xin S et al (2016) Rice husk-derived hierarchical silicon/nitrogen-doped carbon/carbon nanotube spheres as low-cost and high-capacity anodes for lithium-ion batteries. Nano Energy 25:120–127CrossRefGoogle Scholar
  50. 50.
    Niu J, Liang JJ, Shao R et al (2017) Tremella-like N, O-codoped hierarchically porous carbon nanosheets as high-performance anode materials for high energy and ultrafast Na-ion capacitors. Nano Energy 41:285–292CrossRefGoogle Scholar
  51. 51.
    Kumar P, Barrett DM, Delwiche MJ, Stroeve P (2009) Methods for pretreatment of lignocellulosic biomass for efficient hydrolysis and biofuel production. Ind Eng Chem Res 48:3713–3729CrossRefGoogle Scholar
  52. 52.
    Zhu YW, Murali S, Stoller MD et al (2011) Carbon-based supercapacitors produced by activation of grapheme. Science 332:1537–1541CrossRefGoogle Scholar
  53. 53.
    Jiang J, Zhu JH, Ai W et al (2014) Evolution of disposable bamboo chopsticks into uniform carbon fibers: a smart strategy to fabricate sustainable anodes for Li-ion batteries. Energy Environ Sci 7:2670–2679CrossRefGoogle Scholar
  54. 54.
    Wang ZH, Qie L, Yuan LX, Zhang WH, Hu XL, Huang YH (2013) Functionalized N-doped interconnected carbon nanofibers as an anode material for sodium-ion storage with excellent performance. Carbon 55:328–334CrossRefGoogle Scholar
  55. 55.
    Zheng YH, Wang YS, Lu YX, Hu YS, Li J (2017) A high-performance sodium-ion battery enhanced by macadamia shell derived hard carbon anode. Nano Energy 39:489–498CrossRefGoogle Scholar
  56. 56.
    Su CY, Xu YP, Zhang WJ, Zhao JW, Tang XH, Tsai CH, Li LJ (2009) Electrical and spectroscopic characterizations of ultra-Large reduced graphene oxide monolayers. Chem Mater 21:5674–5680CrossRefGoogle Scholar
  57. 57.
    Li DD, Ding LX, Chen HB, Wang SQ, Li Z, Zhu M, Wang HH (2014) Novel nitrogen-rich porous carbon spheres as a high-performance anode material for lithium-ion batteries. J Mater Chem A 2:16617–16622CrossRefGoogle Scholar
  58. 58.
    Xiao LF, Lu HY, Fang YJ et al (2018) Low-defect and low-porosity hard carbon with high coulombic efficiency and high capacity for practical sodium ion battery anode. Adv Energy Mater 8:1703238CrossRefGoogle Scholar
  59. 59.
    Li Y, Zhao Y, Cheng HH, Hu Y, Shi GQ, Dai LM, Qu LT (2011) Nitrogen-doped graphene quantum dots with oxygen-rich functional groups. J Am Chem Soc 134:15–18CrossRefGoogle Scholar
  60. 60.
    Fang Y, Luo B, Jia Y, Li X, Wang B, Song Q (2012) Renewing functionalized graphene as electrodes for high-performance supercapacitor. Adv Mater 24:6348–6355CrossRefGoogle Scholar
  61. 61.
    Ding J, Wang HL, Li Z et al (2015) Peanut shell hybrid sodium ion capacitor with extreme energy–power rivals lithium ion capacitors. Energy Environ Sci 8:941–955CrossRefGoogle Scholar
  62. 62.
    Shao YY, Xiao J, Wang W et al (2013) Surface-driven sodium ion energy storage in nanocellular carbon foams. Nano Lett 13:3909–3914CrossRefGoogle Scholar
  63. 63.
    Peng H, Ma G, Sun K, Mu J, Lei Z (2014) One-step preparation of ultrathin nitrogen-doped carbon nanosheets with ultrahigh pore volume for high-performance supercapacitors. J Mater Chem A 2:17297–17301CrossRefGoogle Scholar
  64. 64.
    Peng H, Ma GF, Sun KJ, Zhang ZG, Yang Q, Lei ZQ (2016) Nitrogen-doped interconnected carbon nanosheets from pomelo mesocarps for high performance supercapacitors. Electrochim Acta 190:862–871CrossRefGoogle Scholar
  65. 65.
    Shen W, Wang C, Xu QJ, Liu HM, Wang YG (2014) Nitrogen-doping-induced defects of a carbon coating layer facilitate Na-storage in electrode materials. Adv Energy Mater 5:1400982CrossRefGoogle Scholar
  66. 66.
    Ding J, Li Z, Cui K, Boyer S, Karpuzov D, Mitlin D (2016) Heteroatom enhanced sodium ion capacity and rate capability in a hydrogel derived carbon give record performance in a hybrid ion capacitor. Nano Energy 23:129–137CrossRefGoogle Scholar
  67. 67.
    DatsyukV Kalyva M, Papagelis K et al (2008) Chemical oxidation of multiwalled carbon nanotubes. Carbon 46:833–840CrossRefGoogle Scholar
  68. 68.
    Shao Y, Zhang S, Engelhard MH et al (2010) Nitrogen-doped graphene and its electrochemical applications. J Mater Chem 20:7491–7496CrossRefGoogle Scholar
  69. 69.
    Sun N, Liu H, Xu B (2015) Facile synthesis of high performance hard carbon anode materials for sodium ion batteries. J Mater Chem A 3:20560–20566CrossRefGoogle Scholar
  70. 70.
    Li YM, Hu YS, Titirici M, Chen LQ, Huang XJ (2016) Hard carbon microtubes made from renewable cotton as high-performance anode material for sodium-ion batteries. Adv Energy Mater 6:1600659CrossRefGoogle Scholar
  71. 71.
    Luo XF, Yang CH, Peng YY, Pu NW, Ger MD, Hsieh CT, Chang JK (2015) Graphene nanosheets, carbon nanotubes, graphite, and activated carbon as anode materials for sodium-ion batteries. J Mater Chem A 3:10320–10326CrossRefGoogle Scholar
  72. 72.
    Li DD, Chen HB, Liu GX, Wei M, Ding LX, Wang SQ, Wang HH (2015) Porous nitrogen doped carbon sphere as high performance anode of sodium-ion battery. Carbon 94:888–894CrossRefGoogle Scholar
  73. 73.
    Qiu S, Xiao LF, Sushko ML et al (2017) Manipulating adsorption–insertion mechanisms in nanostructured carbon materials for high-efficiency sodium ion storage. Adv Energy Mater 7:1700403CrossRefGoogle Scholar
  74. 74.
    Yan D, Yu CY, Zhang XZ et al (2016) Nitrogen-doped carbon microspheres derived from oatmeal as high capacity and superior long life anode material for sodium ion battery. Electrochim Acta 191:385–391CrossRefGoogle Scholar
  75. 75.
    Fu LJ, Tang K, Song KP, van Aken PA, Yu Y, Maier J (2014) Nitrogen doped porous carbon fibres as anode materials for sodium ion batteries with excellent rate performance. Nanoscale 6:1384–1389CrossRefGoogle Scholar
  76. 76.
    Wang PZ, Qiao B, Du YC, Li YF, Zhou XS, Dai ZH, Bao JC (2015) Fluorine-doped carbon particles derived from lotus petioles as high-performance anode materials for sodium-ion batteries. J Phys Chem C 119:21336–21344CrossRefGoogle Scholar
  77. 77.
    Chen L, Wang Z, He C, Zhao N, Shi C, Liu E, Li J (2013) Porous graphitic carbon nanosheets as a high-rate anode material for lithium-ion batteries. ACS Appl Mater Interfaces 5:9537–9545CrossRefGoogle Scholar
  78. 78.
    Niu J, Zhang S, Niu Y, Song HH, Chen XH, Zhou JS, Cao B (2015) Direct amination of Si nanoparticles for the preparation of Si @ ultrathin SiOx @ graphene nanosheets as high performance lithium-ion battery anodes. J Mater Chem A 3:19892–19900CrossRefGoogle Scholar
  79. 79.
    Nakajima T, Gupta V, Ohzawa Y, Groult H, Mazej Z, Žemva B (2004) Influence of cointercalated HF on the electrochemical behavior of highly fluorinated graphite. J Power Sources 137:80–87CrossRefGoogle Scholar
  80. 80.
    Xiao LF, Cao YL, Henderson WA et al (2016) Hard carbon nanoparticles as high-capacity, high-stability anodic materials for Na-ion batteries. Nano Energy 19:279–288CrossRefGoogle Scholar
  81. 81.
    Wang QQ, Zhu XS, Liu YH, Fang YY, Zhou XS, Bao JC (2017) Rice husk-derived hard carbons as high-performance anode materials for sodium-ion batteries. Carbon 127:658–666CrossRefGoogle Scholar
  82. 82.
    Yan D, Yu C, Zhang X, Li J, Li J, Lu T, Pan L (2017) Enhanced electrochemical performances of anatase TiO2 nanotubes by synergetic doping of Ni and N for sodium-ion batteries. Electrochim Acta 254:130–139CrossRefGoogle Scholar
  83. 83.
    Hou HS, Banks CE, JingM Zhang Y, Ji XB (2015) Carbon quantum dots and their derivative 3D porous carbon frameworks for sodium-ion batteries with ultralong cycle life. Adv Mater 27:7861–7866CrossRefGoogle Scholar

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Authors and Affiliations

  1. 1.Shandong Peninsula Engineering Research Center of Comprehensive Brine UtilizationWeifang University of Science and TechnologyShouguangPeople’s Republic of China

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