In Operando Probing of Lithium‐Ion Storage on Single‐Layer Graphene

Despite high‐surface area carbons, e.g., graphene‐based materials, being investigated as anodes for lithium (Li)‐ion batteries, the fundamental mechanism of Li‐ion storage on such carbons is insufficiently understood. In this work, the evolution of the electrode/electrolyte interface is probed on a single‐layer graphene (SLG) film by performing Raman spectroscopy and Fourier transform infrared spectroscopy when the SLG film is electrochemically cycled as the anode in a half cell. The utilization of SLG eliminates the inevitable intercalation of Li ions in graphite or few‐layer graphene, which may have complicated the discussion in previous work. Combining the in situ studies with ex situ observations and ab initio simulations, the formation of solid electrolyte interphase and the structural evolution of SLG are discussed when the SLG is biased in an electrolyte. This study provides new insights into the understanding of Li‐ion storage on SLG and suggests how high‐surface‐area carbons could play proper roles in anodes for Li‐ion batteries.

[1]  Tongchao Liu,et al.  In situ quantification of interphasial chemistry in Li-ion battery , 2018, Nature Nanotechnology.

[2]  A. Krasheninnikov,et al.  Reversible superdense ordering of lithium between two graphene sheets , 2018, Nature.

[3]  Jiangbin Wu,et al.  Raman spectroscopy of graphene-based materials and its applications in related devices. , 2018, Chemical Society reviews.

[4]  Ji‐Guang Zhang,et al.  New Insights on the Structure of Electrochemically Deposited Lithium Metal and Its Solid Electrolyte Interphases via Cryogenic TEM. , 2017, Nano letters.

[5]  Huaihe Song,et al.  Fabrication of hierarchical porous carbon microspheres using porous layered double oxide templates for high-performance lithium ion batteries , 2017 .

[6]  A. Mukhopadhyay,et al.  Understanding the Li-storage in few layers graphene with respect to bulk graphite: experimental, analytical and computational study , 2017 .

[7]  Ya‐Xia Yin,et al.  Stable Li Plating/Stripping Electrochemistry Realized by a Hybrid Li Reservoir in Spherical Carbon Granules with 3D Conducting Skeletons. , 2017, Journal of the American Chemical Society.

[8]  Xiaoqing Yang,et al.  High performance anode of lithium-ion batteries derived from an advanced carbonaceous porous network , 2017 .

[9]  Xinyang Yue,et al.  Macro-mesoporous hollow carbon spheres as anodes for lithium-ion batteries with high rate capability and excellent cycling performance , 2016 .

[10]  Debasish Mohanty,et al.  The state of understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI) and its relationship to formation cycling , 2016 .

[11]  J. Rodríguez‐López,et al.  Layer Number Dependence of Li(+) Intercalation on Few-Layer Graphene and Electrochemical Imaging of Its Solid-Electrolyte Interphase Evolution. , 2016, ACS nano.

[12]  Bingbing Tian,et al.  In Situ Raman and Nuclear Magnetic Resonance Study of Trapped Lithium in the Solid Electrolyte Interface of Reduced Graphene Oxide , 2016 .

[13]  Tokyo,et al.  Structural analysis of polycrystalline graphene systems by Raman spectroscopy , 2015, 1511.06659.

[14]  N. Zheng,et al.  Hierarchical porous carbon microrods composed of vertically aligned graphene-like nanosheets for Li-ion batteries , 2015 .

[15]  Phl Peter Notten,et al.  In situ methods for Li-ion battery research : a review of recent developments , 2015 .

[16]  C. Kvarnström,et al.  In situ FTIR and Raman spectroelectrochemical characterization of graphene oxide upon electrochemical reduction in organic solvents. , 2015, Physical chemistry chemical physics : PCCP.

[17]  Laurence J Hardwick,et al.  In situ Raman study of lithium-ion intercalation into microcrystalline graphite. , 2014, Faraday discussions.

[18]  J. Greeley,et al.  First-principles analysis of defect-mediated Li adsorption on graphene. , 2014, ACS applied materials & interfaces.

[19]  Li-Ming Wu,et al.  First-principles studies of lithium adsorption and diffusion on graphene with grain boundaries , 2014 .

[20]  J. Greeley,et al.  Defect evolution in graphene upon electrochemical lithiation. , 2014, ACS applied materials & interfaces.

[21]  G. Lacconi,et al.  On the Nature of Defects in Liquid-Phase Exfoliated Graphene , 2014, 1409.1548.

[22]  Yongfeng Li,et al.  Controllable growth of 1–7 layers of graphene by chemical vapour deposition , 2014, 1406.2159.

[23]  Yalin Lu,et al.  Capacitance of carbon-based electrical double-layer capacitors , 2014, Nature Communications.

[24]  Xiao Hua,et al.  Origin of additional capacities in metal oxide lithium-ion battery electrodes. , 2013, Nature materials.

[25]  Daniel M. Seo,et al.  Role of Solution Structure in Solid Electrolyte Interphase Formation on Graphite with LiPF6 in Propylene Carbonate , 2013 .

[26]  De‐Yin Wu,et al.  Interfacial capacitance of graphene: Correlated differential capacitance and in situ electrochemical Raman spectroscopy study , 2013 .

[27]  Petr Novák,et al.  Characterization of a model solid electrolyte interphase/carbon interface by combined in situ Raman/Fourier transform infrared microscopy , 2013 .

[28]  Cinzia Casiraghi,et al.  Raman study on defective graphene: Effect of the excitation energy, type, and amount of defects , 2013 .

[29]  D. Zhao,et al.  Two-dimensional mesoporous carbon nanosheets and their derived graphene nanosheets: synthesis and efficient lithium ion storage. , 2013, Journal of the American Chemical Society.

[30]  Li‐Ming Wu,et al.  First-Principles Study of Lithium Adsorption and Diffusion on Graphene with Point Defects , 2012 .

[31]  K. Persson,et al.  Li absorption and intercalation in single layer graphene and few layer graphene by first principles. , 2012, Nano letters.

[32]  Cinzia Casiraghi,et al.  Probing the nature of defects in graphene by Raman spectroscopy. , 2012, Nano letters.

[33]  J. Kuo,et al.  Adsorption and diffusion of Li on pristine and defective graphene. , 2012, ACS applied materials & interfaces.

[34]  Volker L. Deringer,et al.  Crystal orbital Hamilton population (COHP) analysis as projected from plane-wave basis sets. , 2011, The journal of physical chemistry. A.

[35]  A. Krasheninnikov,et al.  Structural defects in graphene. , 2011, ACS nano.

[36]  L. Kavan,et al.  The influence of strong electron and hole doping on the Raman intensity of chemical vapor-deposition graphene. , 2010, ACS nano.

[37]  Robert Kostecki,et al.  The interaction of Li+ with single-layer and few-layer graphene. , 2010, Nano letters.

[38]  Steven G. Louie,et al.  Topological defects in graphene: Dislocations and grain boundaries , 2010, 1004.2031.

[39]  M. Dresselhaus,et al.  Perspectives on carbon nanotubes and graphene Raman spectroscopy. , 2010, Nano letters.

[40]  R. Piner,et al.  Transfer of large-area graphene films for high-performance transparent conductive electrodes. , 2009, Nano letters.

[41]  Joachim Maier,et al.  Lithium Storage in Carbon Nanostructures , 2009, Advanced materials.

[42]  S. Banerjee,et al.  Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils , 2009, Science.

[43]  K. Novoselov,et al.  Control of Graphene's Properties by Reversible Hydrogenation: Evidence for Graphane , 2008, Science.

[44]  E. Akturk,et al.  High-capacity hydrogen storage by metallized graphene , 2008, 0901.1944.

[45]  H. R. Krishnamurthy,et al.  Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor. , 2007, Nature nanotechnology.

[46]  Andre K. Geim,et al.  Raman spectrum of graphene and graphene layers. , 2006, Physical review letters.

[47]  J. Jamnik,et al.  Nanocrystallinity effects in lithium battery materials , 2003 .

[48]  J. Kerr,et al.  From molecular models to system analysis for lithium battery electrolytes , 2002 .

[49]  D. Aurbach,et al.  The study of the anodic stability of alkyl carbonate solutions by in situ FTIR spectroscopy, EQCM, NMR and MS , 2001 .

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

[51]  C. Wan,et al.  Composition analysis of the passive film on the carbon electrode of a lithium-ion battery with an EC-based electrolyte , 1998 .

[52]  T. Ohsaki,et al.  7Li NMR and ESR analysis of lithium storage in a high-capacity perylene-based disordered carbon , 1997 .

[53]  D. Aurbach,et al.  SIMULTANEOUS MEASUREMENTS AND MODELING OF THE ELECTROCHEMICAL IMPEDANCE AND THE CYCLIC VOLTAMMETRIC CHARACTERISTICS OF GRAPHITE ELECTRODES DOPED WITH LITHIUM , 1997 .

[54]  M. Endo,et al.  A Mechanism of Lithium Storage in Disordered Carbons , 1994, Science.

[55]  Axel D. Becke,et al.  A Simple Measure of Electron Localization in Atomic and Molecular-Systems , 1990 .

[56]  Simona Badilescu,et al.  In situ Raman spectroscopic–electrochemical studies of lithium-ion battery materials: a historical overview , 2013, Journal of Applied Electrochemistry.

[57]  G. Radhakrishnan,et al.  Fabrication and Electrochemical Characterization of Single and Multi-Layer Graphene Anodes for Lithium-Ion Batteries , 2012 .

[58]  S. Pyun,et al.  The effect of electrolyte temperature on the passivity of solid electrolyte interphase formed on a graphite electrode , 2002 .

[59]  Minoru Inaba,et al.  In situ Raman study on electrochemical Li intercalation into graphite , 1995 .