Expanded graphite as superior anode for sodium-ion batteries

Graphite, as the most common anode for commercial Li-ion batteries, has been reported to have a very low capacity when used as a Na-ion battery anode. It is well known that electrochemical insertion of Na(+) into graphite is significantly hindered by the insufficient interlayer spacing. Here we report expanded graphite as a Na-ion battery anode. Prepared through a process of oxidation and partial reduction on graphite, expanded graphite has an enlarged interlayer lattice distance of 4.3 Å yet retains an analogous long-range-ordered layered structure to graphite. In situ transmission electron microscopy has demonstrated that the Na-ion can be reversibly inserted into and extracted from expanded graphite. Galvanostatic studies show that expanded graphite can deliver a high reversible capacity of 284 mAh g(-1) at a current density of 20 mA g(-1), maintain a capacity of 184 mAh g(-1) at 100 mA g(-1), and retain 73.92% of its capacity after 2,000 cycles.

[1]  DiVincenzo,et al.  Cohesion and structure in stage-1 graphite intercalation compounds. , 1985, Physical review. B, Condensed matter.

[2]  Bruce Dunn,et al.  High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance. , 2013, Nature materials.

[3]  Seong-Ho Yoon,et al.  Anodic performance and mechanism of mesophase-pitch-derived carbons in lithium ion batteries , 1998 .

[4]  J. Yamaki,et al.  Electrochemical and thermal properties of hard carbon-type anodes for Na-ion batteries , 2013 .

[5]  W. L. Worrell,et al.  A thermodynamic study of sodium-intercalated TaS2 and TiS2 , 1979 .

[6]  Linghui Yu,et al.  Hollow Carbon Nanospheres with Superior Rate Capability for Sodium‐Based Batteries , 2012 .

[7]  Doron Aurbach,et al.  The study of Li-graphite intercalation processes in several electrolyte systems using in situ X-ray diffraction , 1995 .

[8]  S. Dou,et al.  Reduced graphene oxide with superior cycling stability and rate capability for sodium storage , 2013 .

[9]  Imre Dékány,et al.  Evolution of surface functional groups in a series of progressively oxidized graphite oxides , 2006 .

[10]  Y. Ishii,et al.  Progress in 13C and 1H solid-state nuclear magnetic resonance for paramagnetic systems under very fast magic angle spinning. , 2008, The Journal of chemical physics.

[11]  P. Hagenmuller,et al.  Electronic and electrochemical properties of NaxCoO2−y cathode , 1983 .

[12]  W. S. Hummers,et al.  Preparation of Graphitic Oxide , 1958 .

[13]  K. Sing,et al.  Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Provisional) , 1982 .

[14]  P. Hagenmuller,et al.  Electrochemical intercalation of sodium in NaxCoO2 bronzes , 1981 .

[15]  DiVincenzo Dp,et al.  Cohesion and structure in stage-1 graphite intercalation compounds. , 1985 .

[16]  Yuyan Shao,et al.  Surface-driven sodium ion energy storage in nanocellular carbon foams. , 2013, Nano letters.

[17]  J. Dahn,et al.  High‐Capacity Carbons Prepared from Phenolic Resin for Anodes of Lithium‐Ion Batteries , 1995 .

[18]  J. Dahn,et al.  Optimizing Pyrolysis of Sugar Carbons for Use as Anode Materials in Lithium‐Ion Batteries , 1996 .

[19]  Kazuma Gotoh,et al.  NMR study for electrochemically inserted Na in hard carbon electrode of sodium ion battery , 2013 .

[20]  Jun Liu,et al.  Sodium ion insertion in hollow carbon nanowires for battery applications. , 2012, Nano letters.

[21]  Wei Gao,et al.  New insights into the structure and reduction of graphite oxide. , 2009, Nature chemistry.

[22]  Philipp Adelhelm,et al.  Room-temperature sodium-ion batteries: Improving the rate capability of carbon anode materials by templating strategies , 2011 .

[23]  Utsumi,et al.  High-pressure in situ x-ray-diffraction study of the phase transformation from graphite to hexagonal diamond at room temperature. , 1992, Physical review. B, Condensed matter.

[24]  M. Fouletier,et al.  Electrochemical intercalation of sodium in graphite , 1988 .

[25]  P. Novák,et al.  Correlations between surface properties of graphite and the first cycle specific charge loss in lithium-ion batteries , 2009 .

[26]  D. Stevens,et al.  High Capacity Anode Materials for Rechargeable Sodium‐Ion Batteries , 2000 .

[27]  Jacek Klinowski,et al.  Structure of Graphite Oxide Revisited , 1998 .

[28]  R. Piner,et al.  NMR-Based Structural Modeling of Graphite Oxide Using Multidimensional 13C Solid-State NMR and ab Initio Chemical Shift Calculations , 2010, Journal of the American Chemical Society.

[29]  Y. Ishii,et al.  A new approach in 1D and 2D 13C high-resolution solid-state NMR spectroscopy of paramagnetic organometallic complexes by very fast magic-angle spinning. , 2003, Journal of the American Chemical Society.

[30]  S. Ardizzone,et al.  "Inner" and "outer" active surface of RuO2 electrodes , 1990 .

[31]  K. Schmidt-Rohr,et al.  A simple scheme for probehead background suppression in one-pulse 1H NMR. , 2004, Solid state nuclear magnetic resonance.

[32]  Jeff Dahn,et al.  Lithium Insertion in Hydrogen-Containing Carbonaceous Materials , 1996 .

[33]  R. McCreery,et al.  Raman Spectroscopy of Carbon Materials: Structural Basis of Observed Spectra , 1990 .

[34]  D. Stevens,et al.  The Mechanisms of Lithium and Sodium Insertion in Carbon Materials , 2001 .

[35]  A. Goñi,et al.  High capacity hard carbon anodes for sodium ion batteries in additive free electrolyte , 2013 .

[36]  Dongmin Chen,et al.  Synthesis and Solid-State NMR Structural Characterization of 13C-Labeled Graphite Oxide , 2008, Science.

[37]  James Sangster.  C—Na (Carbon—Sodium) System , 2008 .

[38]  Gaoping Cao,et al.  What is the choice for supercapacitors: graphene or graphene oxide? , 2011 .