New Mechanistic Insights on Na-Ion Storage in Nongraphitizable Carbon.

Nongraphitizable carbon, also known as hard carbon, is considered one of the most promising anodes for the emerging Na-ion batteries. The current mechanistic understanding of Na-ion storage in hard carbon is based on the "card-house" model first raised in the early 2000s. This model describes that Na-ion insertion occurs first through intercalation between graphene sheets in turbostratic nanodomains, followed by Na filling of the pores in the carbon structure. We tried to test this model by tuning the sizes of turbostratic nanodomains but revealed a correlation between the structural defects and Na-ion storage. Based on our experimental data, we propose an alternative perspective for sodiation of hard carbon that consists of Na-ion storage at defect sites, by intercalation and last via pore-filling.

[1]  Ricardo Alcántara,et al.  Carbon Microspheres Obtained from Resorcinol-Formaldehyde as High-Capacity Electrodes for Sodium-Ion Batteries , 2005 .

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

[3]  J. Fischer,et al.  Layer disorder in carbon anodes , 1997 .

[4]  Yang-Kook Sun,et al.  Challenges facing lithium batteries and electrical double-layer capacitors. , 2012, Angewandte Chemie.

[5]  Xiang‐qian Shen,et al.  N-substituted defective graphene sheets: promising electrode materials for Na-ion batteries , 2015 .

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

[7]  H. C. Foley,et al.  Local structure of nanoporous carbons , 1999 .

[8]  D. Stevens,et al.  An In Situ Small‐Angle X‐Ray Scattering Study of Sodium Insertion into a Nanoporous Carbon Anode Material within an Operating Electrochemical Cell , 2000 .

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

[10]  B. Warren X-Ray Diffraction in Random Layer Lattices , 1941 .

[11]  M. Inagaki,et al.  Graphitization of carbon fibre/ glassy carbon composites , 1974 .

[12]  Huanlei Wang,et al.  Carbon nanosheet frameworks derived from peat moss as high performance sodium ion battery anodes. , 2013, ACS nano.

[13]  Simon J. L. Billinge,et al.  Underneath the Bragg Peaks: Structural Analysis of Complex Materials , 2003 .

[14]  Jean-Noël Rouzaud,et al.  Comparative XRD, Raman, and TEM study on graphitization of PBO-derived carbon fibers , 2012 .

[15]  Pier Paolo Prosini,et al.  Determination of the chemical diffusion coefficient of lithium in LiFePO4 , 2002 .

[16]  R. Huggins,et al.  Electrochemical investigation of the chemical diffusion, partial ionic conductivities, and other kinetic parameters in Li3Sb and Li3Bi , 1977 .

[17]  D. Keen A comparison of various commonly used correlation functions for describing total scattering , 2001 .

[18]  J. Robertson,et al.  Raman spectroscopy of amorphous, nanostructured, diamond–like carbon, and nanodiamond , 2004, Philosophical Transactions of the Royal Society of London. Series A: Mathematical, Physical and Engineering Sciences.

[19]  Jia Ding,et al.  High-density sodium and lithium ion battery anodes from banana peels. , 2014, ACS nano.

[20]  Christopher M Wolverton,et al.  Electrical energy storage for transportation—approaching the limits of, and going beyond, lithium-ion batteries , 2012 .

[21]  Vivek B Shenoy,et al.  Defective graphene as a high-capacity anode material for Na- and Ca-ion batteries. , 2014, ACS applied materials & interfaces.

[22]  Morinobu Endo,et al.  Graphite Intercalation Compounds and Applications , 2003 .

[23]  Marca M. Doeff,et al.  Electrochemical Insertion of Sodium into Carbon , 1993 .

[24]  Clement Bommier,et al.  Recent Development on Anodes for Na‐Ion Batteries , 2015 .

[25]  Denis Billaud,et al.  Electrochemical insertion of sodium into hard carbons , 2002 .

[26]  Kai He,et al.  Expanded graphite as superior anode for sodium-ion batteries , 2014, Nature Communications.

[27]  Ado Jorio,et al.  General equation for the determination of the crystallite size La of nanographite by Raman spectroscopy , 2006 .

[28]  Yuesheng Wang,et al.  Amorphous monodispersed hard carbon micro-spherules derived from biomass as a high performance negative electrode material for sodium-ion batteries , 2015 .

[29]  Gerbrand Ceder,et al.  Challenges for Na-ion Negative Electrodes , 2011 .

[30]  A. Boldyrev,et al.  Is graphene aromatic? , 2012, Nano Research.

[31]  Kai Cui,et al.  Peanut shell hybrid sodium ion capacitor with extreme energy–power rivals lithium ion capacitors , 2015 .

[32]  Liquan Chen,et al.  Room-temperature stationary sodium-ion batteries for large-scale electric energy storage , 2013 .

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

[34]  Sergei Manzhos,et al.  A computational study of Na behavior on graphene , 2015 .

[35]  Atsuo Yamada,et al.  Ab initio study of sodium intercalation into disordered carbon , 2015 .

[36]  Donghan Kim,et al.  Sodium‐Ion Batteries , 2013 .

[37]  R. Franklin Crystallite growth in graphitizing and non-graphitizing carbons , 1951, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[38]  Shinichi Komaba,et al.  Research development on sodium-ion batteries. , 2014, Chemical reviews.

[39]  Gerbrand Ceder,et al.  Electrode Materials for Rechargeable Sodium‐Ion Batteries: Potential Alternatives to Current Lithium‐Ion Batteries , 2012 .

[40]  Yasuharu Okamoto,et al.  Density Functional Theory Calculations of Alkali Metal (Li, Na, and K) Graphite Intercalation Compounds , 2014 .

[41]  T. Grande,et al.  Van der Waals density functional study of the energetics of alkali metal intercalation in graphite , 2014 .

[42]  J. Robertson,et al.  Interpretation of Raman spectra of disordered and amorphous carbon , 2000 .