Fluorine-Doped Hard Carbon as the Advanced Performance Anode Material of Sodium-Ion Batteries

Abstract

F-doping hard carbon (F–HC) was synthesized through a mild fluorination at temperature at relative low temperature as the potential anode for sodium-ion batteries (SIBs). The F-doping treatment to HC expands interlayer distance and creates some defects in the graphitic framework, which has the ability to improve Na⁺ storage capability through the intercalation and pore-filling process a simultaneously. In addition, the electrically conductive semi-ionic C–F bond in F–HC that can be adjusted by the fluorination temperature facilitates electron transport throughout the electrode. Therefore, F–HC exhibits higher specific capability and better cycling stability than pristine HC. Particularly, F–HC fluorinated at 100 °C (F–HC100) delivers the reversible capability of 343 mAh/g at 50 mAh/g, with the Coulombic efficiency of 78.13%, and the capacity retention remains as 95.81% after 100 cycles. Moreover, the specific capacity of F–HC100 returns to 340 mAh/g after the rate capability test demonstrates its stability even at high current density. The enhanced specific capacity of F–HC, especially at low-voltage region, has the great potential as the anode of SIBs with high energy density.

Keywords

Hard carbon / Fluorine doping / Semi-ionic C–F bond / Sodium-ion batteries

References

[1] Larcher D, Tarascon JM Towards greener and more sustainable batteries for electrical energy storage. Nat Chem, 2015, 7(1): 19-29.

[2] Palomares V, Serras P, Villaluenga I, et al. Na-ion batteries, recent advances and present challenges to become low cost energy storage systems. Energy Environ Sci, 2012, 5(3): 5884.

[3] Pan HL, Hu YS, Chen LQ Room-temperature stationary sodium-ion batteries for large-scale electric energy storage. Energy Environ Sci, 2013, 6(8): 2338.

[4] Goodenough JB, Park KS The Li-ion rechargeable battery: a perspective. J Am Chem Soc, 2013, 135(4): 1167-1176.

[5] Kim SW, Seo DH, Ma XH, et al. Electrode materials for rechargeable sodium-ion batteries: potential alternatives to current lithium-ion batteries. Adv Energy Mater, 2012, 2(7): 710-721.

[6] Slater MD, Kim D, Lee E, et al. Sodium-ion batteries. Adv Funct Mater, 2013, 23(8): 947-958.

[7] Liu YY, Merinov BV, Goddard WA III Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals. PNAS, 2016, 113(14): 3735-3739.

[8] Moriwake H, Kuwabara A, Fisher CAJ, et al. Why is sodium-intercalated graphite unstable?. RSC Adv, 2017, 7(58): 36550-36554.

[9] Li L, Zheng Y, Zhang SL, et al. Recent progress on sodium ion batteries: potential high-performance anodes. Energy Environ Sci, 2018, 11(9): 2310-2340.

[10] Sun Y, Guo SH, Zhou HS Exploration of advanced electrode materials for rechargeable sodium-ion batteries. Adv Energy Mater, 2019, 9(23): 1800212.

[11] Perveen T, Siddiq M, Shahzad N, et al. Prospects in anode materials for sodium ion batteries - a review. Renew Sustain Energy Rev, 2020, 119: 109549.

[12] Hou HS, Qiu XQ, Wei WF, et al. Carbon anode materials for advanced sodium-ion batteries. Adv Energy Mater, 2017, 7(24): 1602898.

[13] Thomas P, Billaud D Electrochemical insertion of sodium into hard carbons. Electrochim Acta, 2002, 47(20): 3303-3307.

[14] Xiao B, Rojo T, Li X Hard carbon as sodium-ion battery anodes: progress and challenges. Chemsuschem, 2019, 12(1): 133-144.

[15] Bai PX, He YW, Zou XX, et al. Elucidation of the sodium-storage mechanism in hard carbons. Adv Energy Mater, 2018, 8(15): 1703217.

[16] Qiu S, Xiao LF, Sushko ML, et al. Manipulating adsorption–insertion mechanisms in nanostructured carbon materials for high-efficiency sodium ion storage. Adv Energy Mater, 2017, 7(17): 1700403.

[17] Alvin S, Yoon D, Chandra C, et al. Revealing sodium ion storage mechanism in hard carbon. Carbon, 2019, 145: 67-81.

[18] Xiao LF, Cao YL, Xiao J, et al. High capacity, reversible alloying reactions in SnSb/C nanocomposites for Na-ion battery applications. Chem Commun, 2012, 48(27): 3321.

[19] Zhang YF, Pan AQ, Ding L, et al. Nitrogen-doped yolk-shell-structured CoSe/C dodecahedra for high-performance sodium ion batteries. ACS Appl Mater Interfaces, 2017, 9(4): 3624-3633.

[20] Li ZF, Bommier C, Chong ZS, et al. Mechanism of Na-ion storage in hard carbon anodes revealed by heteroatom doping. Adv Energy Mater, 2017, 7(18): 1602894.

[21] Chen SL, Feng F, Ma ZF Lignin-derived nitrogen-doped porous ultrathin layered carbon as a high-rate anode material for sodium-ion batteries. Compos Commun, 2020, 22: 100447.

[22] An HR, Li Y, Feng YY, et al. Reduced graphene oxide doped predominantly with CF2 groups as a superior anode material for long-life lithium-ion batteries. Chem Commun, 2018, 54(22): 2727-2730.

[23] Wang PZ, Qiao B, Du YC, et al. Fluorine-doped carbon particles derived from Lotus petioles as high-performance anode materials for sodium-ion batteries. J Phys Chem C, 2015, 119(37): 21336-21344.

[24] Hong SM, Etacheri V, Hong CN, et al. Enhanced lithium- and sodium-ion storage in an interconnected carbon network comprising electronegative fluorine. ACS Appl Mater Interfaces, 2017, 9(22): 18790-18798.

[25] He QC, Jiang JH, Zhu JL, et al. A facile and cost effective synthesis of nitrogen and fluorine Co-doped porous carbon for high performance Sodium ion battery anode material. J Power Sources, 2020, 448: 227568.

[26] An HR, Li Y, Gao Y, et al. Free-standing fluorine and nitrogen co-doped graphene paper as a high-performance electrode for flexible sodium-ion batteries. Carbon, 2017, 116: 338-346.

[27] Yan XM, Liang ST, Shi HT, et al. Nitrogen-enriched carbon nanofibers with tunable semi-ionic CF bonds as a stable long cycle anode for sodium-ion batteries. J Colloid Interface Sci, 2021, 583: 535-543.

[28] Zhou RX, Li Y, Feng YY, et al. The electrochemical performances of fluorinated hard carbon as the cathode of lithium primary batteries. Compos Commun, 2020, 21: 100396.

[29] Stevens DA, Dahn JR High capacity anode materials for rechargeable sodium-ion batteries. J Electrochem Soc, 2000, 147(4): 1271.

[30] Xu DF, Chen CJ, Xie J, et al. A hierarchical N/S-codoped carbon anode fabricated facilely from cellulose/polyaniline microspheres for high-performance sodium-ion batteries. Adv Energy Mater, 2016, 6(6): 1501929.

[31] Li JF, Han L, Zhang DF, et al. N, S co-doped porous carbon microtubes with high charge/discharge rates for sodium-ion batteries. Inorg Chem Front, 2019, 6(8): 2104-2111.

[32] Sato Y, Itoh K, Hagiwara R, et al. On the so-called “semi-ionic” C-F bond character in fluorine-GIC. Carbon, 2004, 42(15): 3243-3249.

[33] Nair RR, Ren WC, Jalil R, et al. Fluorographene: a two-dimensional counterpart of teflon. Small, 2010, 6(24): 2877-2884.

[34] Park S, Lee KS, Bozoklu G, et al. Graphene oxide papers modified by divalent ions-enhancing mechanical properties via chemical cross-linking. ACS Nano, 2008, 2(3): 572-578.

[35] Lee JM, Kim SJ, Kim JW, et al. A high resolution XPS study of sidewall functionalized MWCNTs by fluorination. J Ind Eng Chem, 2009, 15(1): 66-71.

[36] Wang WZ, Li Y, Feng YY, et al. Asymmetric self-supporting hybrid fluorinated carbon nanotubes/carbon nanotubes sponge electrode for high-performance lithium-polysulfide battery. Chem Eng J, 2018, 349: 756-765.

[37] Chen YL, Li Y, Yao FN, et al. Nitrogen and fluorine co-doped holey graphene hydrogel as a binder-free electrode material for flexible solid-state supercapacitors. Sustain Energy Fuels, 2019, 3(9): 2237-2245.

[38] Li Y, Feng YY, Feng W Deeply fluorinated multi-wall carbon nanotubes for high energy and power densities lithium/carbon fluorides battery. Electrochim Acta, 2013, 107: 343-349.

[39] An HR, Li Y, Long P, et al. Hydrothermal preparation of fluorinated graphene hydrogel for high-performance supercapacitors. J Power Sources, 2016, 312: 146-155.

[40] Lotfabad EM, Ding J, Cui K, et al. High-density sodium and lithium ion battery anodes from banana peels. ACS Nano, 2014, 8(7): 7115-7129.

[41] Stevens DA, Dahn JR The mechanisms of lithium and sodium insertion in carbon materials. J Electrochem Soc, 2001, 148(8): A803.

[42] Gotoh K, Ishikawa T, Shimadzu S, et al. NMR study for electrochemically inserted Na in hard carbon electrode of sodium ion battery. J Power Sources, 2013, 225: 137-140.

[43] Simone V, Boulineau A, de Geyer A, et al. Hard carbon derived from cellulose as anode for sodium ion batteries: dependence of electrochemical properties on structure. J Energy Chem, 2016, 25(5): 761-768.

[44] Song HW, Li N, Cui H, et al. Enhanced storage capability and kinetic processes by pores- and hetero-atoms- riched carbon nanobubbles for lithium-ion and sodium-ion batteries anodes. Nano Energy, 2014, 4: 81-87.

[45] Alvin S, Cahyadi HS, Hwang J, et al. Intercalation mechanisms: revealing the intercalation mechanisms of lithium, sodium, and potassium in hard carbon (adv. energy mater. 20/2020). Adv Energy Mater, 2020, 10(20): 2070093.

[46] Mukherjee R, Thomas AV, Krishnamurthy A, et al. Photothermally reduced graphene as high-power anodes for lithium-ion batteries. ACS Nano, 2012, 6(9): 7867-7878.

[47] Li HM, Wu TT, Chen YY, et al. Self-crosslinked herringbone dihydrophenazine derivatives for high performance organic batteries. Compos Commun, 2021, 28: 100947.

[48] Pol VG, Lee E, Zhou DH, et al. Spherical carbon as a new high-rate anode for sodium-ion batteries. Electrochim Acta, 2014, 127: 61-67.

[49] Shen YL, Sun SJ, Yang M, et al. Typha-derived hard carbon for high-performance sodium ion storage. J Alloy Compd, 2019, 784: 1290-1296.

[50] Li ZF, Ma L, Surta TW, et al. High capacity of hard carbon anode in Na-ion batteries unlocked by POx doping. ACS Energy Lett, 2016, 1(2): 395-401.

[51] Liao WM, Shan ZQ, Tian JH, et al. Facile Fabrication of Fe₃O₄@TiO₂@C Yolk-Shell Spheres as Anode Material for Lithium Ion Batteries. Trans Tianjin Univ, 2020, 26(1): 3-12.

[52] Cao ZJ, Liu HT, Huang WL, et al. Hydrogen bonding-assisted synthesis of silica/oxidized mesocarbon microbeads encapsulated in amorphous carbon as stable anode for optimized/enhanced lithium storage. Trans Tianjin Univ, 2020, 26(1): 13-21.

[53] Yan Y, Ma ZY, Lin HJ, et al. Hydrogel self-templated synthesis of Na₃V₂(PO₄)₃@C@CNT porous network as ultrastable cathode for sodium-ion batteries. Compos Commun, 2019, 13: 97-102.

[54] Tian JJ, Yang H, Fu CM, et al. In-situ synthesis of microspherical Sb@C composite anode with high tap density for lithium/sodium-ion batteries. Compos Commun, 2020, 17: 177-181.

[55] Sun YJ, Zheng JF, Yang Y, et al. Design advanced porous Polyaniline-PEDOT: PSS composite as high performance cathode for sodium ion batteries. Compos Commun, 2021, 24: 100674.