Electronic structure changes upon lithium intercalation into graphite – Insights from ex situ and operando x-ray Raman spectroscopy

Boesenberg, Ulrike; Sokaras, Dimosthenis; Nordlund, Dennis; Weng, Tsu-Chien; Gorelov, Evgeny; Richardson, Thomas J.; Kostecki, Robert; Cabana, Jordi

doi:10.1016/j.carbon.2018.11.031

Title: Electronic structure changes upon lithium intercalation into graphite – Insights from ex situ and operando x-ray Raman spectroscopy

Journal Article · 12 November 2018 · Carbon

DOI: https://doi.org/10.1016/j.carbon.2018.11.031 · OSTI ID:1502989

Boesenberg, Ulrike ^[1]; Sokaras, Dimosthenis ^[2]; Nordlund, Dennis ^[2]; Weng, Tsu-Chien ^[2]; Gorelov, Evgeny ^[3]; Richardson, Thomas J. ^[4]; Kostecki, Robert ^[4]; Cabana, Jordi ^[5]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); European X-Ray Free-Electron Laser Facility, Schenefeld (Germany)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
European X-Ray Free-Electron Laser Facility, Schenefeld (Germany)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of Illinois, Chicago, IL (United States)

This study probes the electrochemical intercalation mechanism of Li into graphitic carbon using x-ray Raman spectroscopy (XRS), an inelastic x-ray scattering technique. Operando and high resolution spectra of electrochemically lithiated composite graphitic electrodes at discrete states of Li uptake (stages III, II and I) show gradually changing spectral features with Li intercalation, the end state agreeing well with chemically fully lithiated LiC₆ highly oriented pyrolytic graphite (HOPG). The two most dominant changes in the XRS spectrum of the C-K edge are the reduced intensity of the $$\pi$$* peak and shift the onset of the σ* states to lower energies upon full lithiation. The excellent instrumental energy resolution uncovered novel spectral features and, thus, electronic changes with varying lithium content. Thus, the general spectral changes with progressing Li intercalation agree well with our accompanying DFT calculations.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-76SF00515; SC0001294

OSTI ID:: 1502989

Journal Information:: Carbon, Journal Name: Carbon Journal Issue: C Vol. 143; ISSN 0008-6223

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (41)

Insertion Electrode Materials for Rechargeable Lithium Batteries Winter, Martin; Besenhard, Jürgen O.; Spahr, Michael E. Advanced Materials, Vol. 10, Issue 10 https://doi.org/10.1002/(SICI)1521-4095(199807)10:10<725::AID-ADMA725>3.0.CO;2-Z	journal	July 1998
Lithium Storage in Carbon Nanostructures Kaskhedikar, Nitin A.; Maier, Joachim Advanced Materials, Vol. 21, Issue 25-26 https://doi.org/10.1002/adma.200901079	journal	July 2009
Tetrakohlenstoffmonofluorid, eine neue Graphit-Fluor-Verbindung Rüdorff, Walter; Rüdorff, Gerda Chemische Berichte, Vol. 80, Issue 5 https://doi.org/10.1002/cber.19470800509	journal	September 1947
X-Ray Interactions: Photoabsorption, Scattering, Transmission, and Reflection at E = 50-30,000 eV, Z = 1-92 Henke, B. L.; Gullikson, E. M.; Davis, J. C. Atomic Data and Nuclear Data Tables, Vol. 54, Issue 2, p. 181-342 https://doi.org/10.1006/adnd.1993.1013	journal	July 1993
Iron speciation in minerals and glasses probed by $$\hbox{M}_{2/3}$$ M 2 / 3 -edge X-ray Raman scattering spectroscopy Nyrow, A.; Sternemann, C.; Wilke, M. Contributions to Mineralogy and Petrology, Vol. 167, Issue 5 https://doi.org/10.1007/s00410-014-1012-8	journal	May 2014
Intercalation of lithium into graphite and other carbons Guerard, D.; Herold, A. Carbon, Vol. 13, Issue 4 https://doi.org/10.1016/0008-6223(75)90040-8	journal	August 1975
Electronic structure of lithium graphite Wertheim, G. K.; Van Attekum, P. T. Th. M.; Basu, S. Solid State Communications, Vol. 33, Issue 11 https://doi.org/10.1016/0038-1098(80)91089-3	journal	March 1980
Interlayer states of LiC6 investigated by inelastic X-ray scattering spectroscopy (IXSS) using Li-core excitation Schülke, W.; Gabriel, K. -J.; Berthold, A. Solid State Communications, Vol. 79, Issue 8 https://doi.org/10.1016/0038-1098(91)90608-X	journal	August 1991
Carbon K-edge X-ray Raman spectroscopy supports simple, yet powerful description of aromatic hydrocarbons and asphaltenes Bergmann, Uwe; Groenzin, Henning; Mullins, Oliver C. Chemical Physics Letters, Vol. 369, Issue 1-2 https://doi.org/10.1016/S0009-2614(02)02003-1	journal	February 2003
Carbon K-edge XANES spectromicroscopy of natural graphite Brandes, Jay A.; Cody, George D.; Rumble, Douglas Carbon, Vol. 46, Issue 11 https://doi.org/10.1016/j.carbon.2008.06.020	journal	September 2008
Density-functional theory calculations of the electron energy-loss near-edge structure of Li-intercalated graphite Titantah, J. T.; Lamoen, D.; Schowalter, M. Carbon, Vol. 47, Issue 10 https://doi.org/10.1016/j.carbon.2009.05.002	journal	August 2009
Hard X-rays in–soft X-rays out: An operando piggyback view deep into a charging lithium ion battery with X-ray Raman spectroscopy Braun, Artur; Nordlund, Dennis; Song, Seung-Wan Journal of Electron Spectroscopy and Related Phenomena, Vol. 200 https://doi.org/10.1016/j.elspec.2015.03.005	journal	April 2015
Understanding structural changes in NMC Li-ion cells by in situ neutron diffraction Dolotko, O.; Senyshyn, A.; Mühlbauer, M. J. Journal of Power Sources, Vol. 255 https://doi.org/10.1016/j.jpowsour.2014.01.010	journal	June 2014
Phase formation and microstructure in lithium-carbon intercalation compounds during lithium uptake and release Drüe, Martin; Seyring, Martin; Rettenmayr, Markus Journal of Power Sources, Vol. 353 https://doi.org/10.1016/j.jpowsour.2017.03.152	journal	June 2017
Bulk-Sensitive Characterization of the Discharged Products in Li–O ₂ Batteries by Nonresonant Inelastic X-ray Scattering Karan, Naba K.; Balasubramanian, Mahalingam; Fister, Timothy T. The Journal of Physical Chemistry C, Vol. 116, Issue 34 https://doi.org/10.1021/jp306298e	journal	August 2012
Lithium Diffusion in Graphitic Carbon Persson, Kristin; Sethuraman, Vijay A.; Hardwick, Laurence J. The Journal of Physical Chemistry Letters, Vol. 1, Issue 8 https://doi.org/10.1021/jz100188d	journal	March 2010
Chemical Distribution and Bonding of Lithium in Intercalated Graphite: Identification with Optimized Electron Energy Loss Spectroscopy Wang, Feng; Graetz, Jason; Moreno, M. Sergio ACS Nano, Vol. 5, Issue 2 https://doi.org/10.1021/nn1028168	journal	January 2011
Structure of graphite by neutron diffraction Trucano, Peter; Chen, Ruey Nature, Vol. 258, Issue 5531 https://doi.org/10.1038/258136a0	journal	November 1975
Tracking lithium transport and electrochemical reactions in nanoparticles Wang, Feng; Yu, Hui-Chia; Chen, Min-Hua Nature Communications, Vol. 3, Issue 1 https://doi.org/10.1038/ncomms2185	journal	January 2012
Solid electrolyte interphase on graphite Li-ion battery anodes studied by soft X-ray spectroscopy Augustsson, A.; Herstedt, M.; Guo, J. -H. Phys. Chem. Chem. Phys., Vol. 6, Issue 16 https://doi.org/10.1039/B313434B	journal	January 2004
Electron energy-loss spectrometry on lithiated graphite Hightower, A.; Ahn, C. C.; Fultz, B. Applied Physics Letters, Vol. 77, Issue 2 https://doi.org/10.1063/1.126936	journal	July 2000
Multielement spectrometer for efficient measurement of the momentum transfer dependence of inelastic x-ray scattering Fister, T. T.; Seidler, G. T.; Wharton, L. Review of Scientific Instruments, Vol. 77, Issue 6 https://doi.org/10.1063/1.2204581	journal	June 2006
Fine structure and chemical shifts in nonresonant inelastic x-ray scattering from Li-intercalated graphite Balasubramanian, M.; Johnson, C. S.; Cross, J. O. Applied Physics Letters, Vol. 91, Issue 3 https://doi.org/10.1063/1.2752755	journal	July 2007
A high resolution and large solid angle x-ray Raman spectroscopy end-station at the Stanford Synchrotron Radiation Lightsource Sokaras, D.; Nordlund, D.; Weng, T. -C. Review of Scientific Instruments, Vol. 83, Issue 4 https://doi.org/10.1063/1.4704458	journal	April 2012
Revealing the electronic structure of LiC ₆ by soft X-ray spectroscopy Zhang, L.; Li, X.; Augustsson, A. Applied Physics Letters, Vol. 110, Issue 10 https://doi.org/10.1063/1.4978432	journal	March 2017
Intercalation stage dependence of core electronic excitations in Li-intercalated graphite from inelastic X-ray scattering Stutz, G. E.; Otero, M.; Ceppi, S. A. Applied Physics Letters, Vol. 110, Issue 25 https://doi.org/10.1063/1.4986922	journal	June 2017
Intercalation compounds of graphite Dresselhaus, M. S.; Dresselhaus, G. Advances in Physics, Vol. 51, Issue 1 https://doi.org/10.1080/00018730110113644	journal	January 2002
Electronic and magnetic properties of the graphene–ferromagnet interface Dedkov, Yu S.; Fonin, M. New Journal of Physics, Vol. 12, Issue 12 https://doi.org/10.1088/1367-2630/12/12/125004	journal	December 2010
Theoretical study of lithium graphite. I. Band structure, density of states, and Fermi-surface properties Holzwarth, N. A. W.; Rabii, S.; Girifalco, L. A. Physical Review B, Vol. 18, Issue 10 https://doi.org/10.1103/PhysRevB.18.5190	journal	November 1978
Theoretical study of lithium graphite. II. Spatial distribution of valence electrons Holzwarth, N. A. W.; Girifalco, L. A.; Rabii, S. Physical Review B, Vol. 18, Issue 10 https://doi.org/10.1103/PhysRevB.18.5206	journal	November 1978
Lithium-intercalated graphite: Self-consistent electronic structure for stages one, two, and three Holzwarth, N. A. W.; Louie, Steven G.; Rabii, Sohrab Physical Review B, Vol. 28, Issue 2 https://doi.org/10.1103/PhysRevB.28.1013	journal	July 1983
Valence and core electronic excitations in Li C 6 Grunes, L. A.; Gates, I. P.; Ritsko, J. J. Physical Review B, Vol. 28, Issue 12 https://doi.org/10.1103/PhysRevB.28.6681	journal	December 1983
Interband transitions and core excitation in highly oriented pyrolytic graphite studied by inelastic synchrotron x-ray scattering: Band-structure information Schülke, W.; Bonse, U.; Nagasawa, H. Physical Review B, Vol. 38, Issue 3 https://doi.org/10.1103/PhysRevB.38.2112	journal	July 1988
Phase diagram of Li x C 6 Dahn, J. R. Physical Review B, Vol. 44, Issue 17 https://doi.org/10.1103/PhysRevB.44.9170	journal	November 1991
Energy-loss near-edge structure changes with bond length in carbon systems Titantah, J. T.; Lamoen, D. Physical Review B, Vol. 72, Issue 19 https://doi.org/10.1103/PhysRevB.72.193104	journal	November 2005
Thermodynamic and kinetic properties of the Li-graphite system from first-principles calculations Persson, Kristin; Hinuma, Yoyo; Meng, Ying Shirley Physical Review B, Vol. 82, Issue 12 https://doi.org/10.1103/PhysRevB.82.125416	journal	September 2010
Evidence for Interlayer Band Shifts upon Lithium Intercalation in Graphite from Inelastic X-Ray Scattering Schülke, W.; Berthold, A.; Kaprolat, A. Physical Review Letters, Vol. 60, Issue 21 https://doi.org/10.1103/PhysRevLett.60.2217	journal	May 1988
Multiple-element spectrometer for non-resonant inelastic X-ray spectroscopy of electronic excitations Verbeni, Roberto; Pylkkänen, Tuomas; Huotari, Simo Journal of Synchrotron Radiation, Vol. 16, Issue 4 https://doi.org/10.1107/S090904950901886X	journal	June 2009
X-ray Raman spectroscopy of lithium-ion battery electrolyte solutions in a flow cell Ketenoglu, Didem; Spiekermann, Georg; Harder, Manuel Journal of Synchrotron Radiation, Vol. 25, Issue 2 https://doi.org/10.1107/S1600577518001662	journal	February 2018
Momentum-Transfer Dependence of the Near Edge Structure of Li Nagasawa, Hisao; Mourikis, Spiridon; Schülke, Winfried Journal of the Physical Society of Japan, Vol. 66, Issue 10 https://doi.org/10.1143/JPSJ.66.3139	journal	October 1997
Comparison of Cycling Performance of Lithium Ion Cell Anode Graphites Ridgway, Paul; Zheng, Honghe; Bello, A. F. Journal of The Electrochemical Society, Vol. 159, Issue 5 https://doi.org/10.1149/2.006205jes	journal	January 2012

Cited By (2)

In situ X-ray Raman spectroscopy and magnetic susceptibility study on the Li[Li _0.15 Mn _1.85 ]O ₄ oxygen anion redox reaction Mukai, Kazuhiko; Nonaka, Takamasa; Uyama, Takeshi Chemical Communications, Vol. 56, Issue 11 https://doi.org/10.1039/c9cc09051g	journal	January 2020
Intercalation chemistry of graphite: alkali metal ions and beyond Li, Yuqi; Lu, Yaxiang; Adelhelm, Philipp Chemical Society Reviews, Vol. 48, Issue 17 https://doi.org/10.1039/c9cs00162j	journal	January 2019

Similar Records

Operando video microscopy of Li plating and re-intercalation on graphite anodes during fast charging

Journal Article · 2021 · Journal of Materials Chemistry. A · OSTI ID:1924793

Chen, Yuxin; Chen, Kuan-Hung; Sanchez, Adrian J.; +6 more

In situ Raman study on electrochemical Li intercalation into graphite

Journal Article · 1994 · Journal of the Electrochemical Society; (United States) · OSTI ID:6542314

Inaba, Minoru; Yoshida, Hiroyuki; Ogumi, Zempachi; +3 more

Direct Evidence of Charge Transfer upon Anion Intercalation in Graphite Cathodes through New Electronic States: An Experimental and Theoretical Study of Hexafluorophosphate

Journal Article · 2020 · Chemistry of Materials · OSTI ID:1632274

de Boer, Tristan; Lapping, Jacob G.; Read, Jeffrey A.; +4 more

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Electronic structure changes upon lithium intercalation into graphite – Insights from ex situ and operando x-ray Raman spectroscopy

Citation Formats

References (41)

Cited By (2)

Similar Records

Related Subjects