Probing microstructure and electrolyte concentration dependent cell chemistry via operando small angle neutron scattering
Abstract
The key to understanding the cycling mechanism of lithium-ion battery electrodes is to develop methods to monitor the dynamic cell chemistry, but the complexity of the problem has continued to pose an obstacle. Here we describe the use of operando small-angle neutron scattering (SANS) to show directly how the use of concentrated LiTFSI electrolyte in Li/ordered mesoporous carbon (OMC) half-cells influences the mechanism of solid electrolyte interphase (SEI) formation, lithium intercalation, and carbon framework expansion. We find that a complex interplay between the viscosity, lithium solvation shell and electrode microstructure in the concentrated 4 M electrolyte changes the dynamics of SEI formation and pore filling at a given applied potential. Both the filling of micropores and co-intercalation are found to drive the expansion of the carbon framework. Lithium-rich reduction products form at much higher potentials in the micropores of the 4 M electrolyte system, while on mesopore surfaces the lithium-rich salts form quickly before giving way to carbonaceous products. As a result, this study reveals operando SANS as a unique method for providing microstructure dependent information on the dynamics of electrochemical processes.
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1543225
- Alternate Identifier(s):
- OSTI ID: 1493369
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Energy & Environmental Science
- Additional Journal Information:
- Journal Volume: 12; Journal Issue: 6; Journal ID: ISSN 1754-5692
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Jafta, Charl J., Sun, Xiao -Guang, Veith, Gabriel M., Jensen, Grethe V., Mahurin, Shannon Mark, Paranthaman, Mariappan P., Dai, Sheng, and Bridges, Craig A. Probing microstructure and electrolyte concentration dependent cell chemistry via operando small angle neutron scattering. United States: N. p., 2019.
Web. doi:10.1039/C8EE02703J.
Jafta, Charl J., Sun, Xiao -Guang, Veith, Gabriel M., Jensen, Grethe V., Mahurin, Shannon Mark, Paranthaman, Mariappan P., Dai, Sheng, & Bridges, Craig A. Probing microstructure and electrolyte concentration dependent cell chemistry via operando small angle neutron scattering. United States. https://doi.org/10.1039/C8EE02703J
Jafta, Charl J., Sun, Xiao -Guang, Veith, Gabriel M., Jensen, Grethe V., Mahurin, Shannon Mark, Paranthaman, Mariappan P., Dai, Sheng, and Bridges, Craig A. Fri .
"Probing microstructure and electrolyte concentration dependent cell chemistry via operando small angle neutron scattering". United States. https://doi.org/10.1039/C8EE02703J. https://www.osti.gov/servlets/purl/1543225.
@article{osti_1543225,
title = {Probing microstructure and electrolyte concentration dependent cell chemistry via operando small angle neutron scattering},
author = {Jafta, Charl J. and Sun, Xiao -Guang and Veith, Gabriel M. and Jensen, Grethe V. and Mahurin, Shannon Mark and Paranthaman, Mariappan P. and Dai, Sheng and Bridges, Craig A.},
abstractNote = {The key to understanding the cycling mechanism of lithium-ion battery electrodes is to develop methods to monitor the dynamic cell chemistry, but the complexity of the problem has continued to pose an obstacle. Here we describe the use of operando small-angle neutron scattering (SANS) to show directly how the use of concentrated LiTFSI electrolyte in Li/ordered mesoporous carbon (OMC) half-cells influences the mechanism of solid electrolyte interphase (SEI) formation, lithium intercalation, and carbon framework expansion. We find that a complex interplay between the viscosity, lithium solvation shell and electrode microstructure in the concentrated 4 M electrolyte changes the dynamics of SEI formation and pore filling at a given applied potential. Both the filling of micropores and co-intercalation are found to drive the expansion of the carbon framework. Lithium-rich reduction products form at much higher potentials in the micropores of the 4 M electrolyte system, while on mesopore surfaces the lithium-rich salts form quickly before giving way to carbonaceous products. As a result, this study reveals operando SANS as a unique method for providing microstructure dependent information on the dynamics of electrochemical processes.},
doi = {10.1039/C8EE02703J},
journal = {Energy & Environmental Science},
number = 6,
volume = 12,
place = {United States},
year = {Fri Jan 25 00:00:00 EST 2019},
month = {Fri Jan 25 00:00:00 EST 2019}
}
Web of Science
Works referenced in this record:
Macroporous Interconnected Hollow Carbon Nanofibers Inspired by Golden-Toad Eggs toward a Binder-Free, High-Rate, and Flexible Electrode
journal, June 2016
- Yin, Yan-Bin; Xu, Ji-Jing; Liu, Qing-Chao
- Advanced Materials, Vol. 28, Issue 34
Review—Superconcentrated Electrolytes for Lithium Batteries
journal, January 2015
- Yamada, Yuki; Yamada, Atsuo
- Journal of The Electrochemical Society, Vol. 162, Issue 14
Observing Framework Expansion of Ordered Mesoporous Hard Carbon Anodes with Ionic Liquid Electrolytes via in Situ Small-Angle Neutron Scattering
journal, June 2017
- Bridges, Craig A.; Sun, Xiao-Guang; Guo, Bingkun
- ACS Energy Letters, Vol. 2, Issue 7
Effect of co-intercalated organic solvents in graphite on electrochemical Li intercalation
journal, November 2001
- Abe, T.; Mizutani, Y.; Kawabata, N.
- Synthetic Metals, Vol. 125, Issue 2
Stable solvates in solution of lithium bis(trifluoromethylsulfone)imide in glymes and other aprotic solvents: Phase diagrams, crystallography and Raman spectroscopyElectronic supplementary information (ESI) available: Crystallographic data (single crystal data) in cif format (CCDC reference number 184345). See http://www.rsc.org/suppdata/cp/b2/b203776a/
journal, November 2002
- Brouillette, Dany; Irish, Donald E.; Taylor, Nicholas J.
- Physical Chemistry Chemical Physics, Vol. 4, Issue 24
Surface Film Formation on Graphite Negative Electrode in Lithium-Ion Batteries: AFM Study in an Ethylene Carbonate-Based Solution
journal, January 2001
- Jeong, Soon-Ki; Inaba, Minoru; Abe, Takeshi
- Journal of The Electrochemical Society, Vol. 148, Issue 9
Severe Loss of Confined Sulfur in Nanoporous Carbon for Li–S Batteries under Wetting Conditions
journal, January 2018
- Scholz, Jonas; Kayaalp, Buğra; Juhl, Anika C.
- ACS Energy Letters, Vol. 3, Issue 2
Tailoring deposition and morphology of discharge products towards high-rate and long-life lithium-oxygen batteries
journal, September 2013
- Xu, Ji-Jing; Wang, Zhong-Li; Xu, Dan
- Nature Communications, Vol. 4, Issue 1
Design of electrolyte solutions for Li and Li-ion batteries: a review
journal, November 2004
- Aurbach, Doron; Talyosef, Yosef; Markovsky, Boris
- Electrochimica Acta, Vol. 50, Issue 2-3
Interfacial reactions between graphite electrodes and propylene carbonate-based solutions: Electrolyte-concentration dependence of electrochemical lithium intercalation reaction
journal, January 2008
- Jeong, Soon-Ki; Inaba, Minoru; Iriyama, Yasutoshi
- Journal of Power Sources, Vol. 175, Issue 1
Distribution of Sulfur in Carbon/Sulfur Nanocomposites Analyzed by Small-Angle X-ray Scattering
journal, March 2016
- Petzold, Albrecht; Juhl, Anika; Scholz, Jonas
- Langmuir, Vol. 32, Issue 11
Electrochemical storage of energy in carbon nanotubes and nanostructured carbons
journal, August 2002
- Frackowiak, Elzbieta; Béguin, François
- Carbon, Vol. 40, Issue 10
Corrosion Prevention Mechanism of Aluminum Metal in Superconcentrated Electrolytes
journal, July 2015
- Yamada, Yuki; Chiang, Ching Hua; Sodeyama, Keitaro
- ChemElectroChem, Vol. 2, Issue 11
Unusual Stability of Acetonitrile-Based Superconcentrated Electrolytes for Fast-Charging Lithium-Ion Batteries
journal, March 2014
- Yamada, Yuki; Furukawa, Keizo; Sodeyama, Keitaro
- Journal of the American Chemical Society, Vol. 136, Issue 13, p. 5039-5046
In Situ AFM Observation of Surface Morphology of Highly Oriented Pyrolytic Graphite in Propylene Carbonate-Based Electrolyte Solutions Containing Lithium and Bivalent Cations
journal, December 2016
- Fukutsuka, Tomokazu; Kokumai, Ryohei; Song, Hee-Youb
- Journal of The Electrochemical Society, Vol. 164, Issue 2
The 30 m Small-Angle Neutron Scattering Instruments at the National Institute of Standards and Technology
journal, June 1998
- Glinka, C. J.; Barker, J. G.; Hammouda, B.
- Journal of Applied Crystallography, Vol. 31, Issue 3, p. 430-445
Correlating Li + Solvation Sheath Structure with Interphasial Chemistry on Graphite
journal, December 2012
- von Wald Cresce, Arthur; Borodin, Oleg; Xu, Kang
- The Journal of Physical Chemistry C, Vol. 116, Issue 50
Electrolyte Solvation and Ionic Association
journal, January 2012
- Seo, Daniel M.; Borodin, Oleg; Han, Sang-Don
- Journal of The Electrochemical Society, Vol. 159, Issue 5
Lithium NMR in Lithium-Carbon Solid State Compounds
journal, January 2000
- Conard, Jacques; Lauginie, Pierre
- TANSO, Vol. 2000, Issue 191
"Water-in-salt" electrolyte enables high-voltage aqueous lithium-ion chemistries
journal, November 2015
- Suo, L.; Borodin, O.; Gao, T.
- Science, Vol. 350, Issue 6263
Correlating Morphological Evolution of Li Electrodes with Degrading Electrochemical Performance of Li/LiCoO 2 and Li/S Battery Systems: Investigated by Synchrotron X-ray Phase Contrast Tomography
journal, January 2018
- Sun, Fu; Osenberg, Markus; Dong, Kang
- ACS Energy Letters, Vol. 3, Issue 2
Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review
journal, July 2017
- Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi
- Chemical Reviews, Vol. 117, Issue 15
Electrochemistry and Structural Chemistry of LiNiO[sub 2] (R3m) for 4 Volt Secondary Lithium Cells
journal, January 1993
- Ohzuku, Tsutomu
- Journal of The Electrochemical Society, Vol. 140, Issue 7
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004
- Xu, Kang
- Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418
Synthesis of New, Nanoporous Carbon with Hexagonally Ordered Mesostructure
journal, November 2000
- Jun, Shinae; Joo, Sang Hoon; Ryoo, Ryong
- Journal of the American Chemical Society, Vol. 122, Issue 43
Co-embedded N-doped carbon fibers as highly efficient and binder-free cathode for Na–O 2 batteries
journal, January 2017
- Ma, Jin-Ling; Meng, Fan-Lu; Xu, Dan
- Energy Storage Materials, Vol. 6
Non-flammable electrolytes with high salt-to-solvent ratios for Li-ion and Li-metal batteries
journal, July 2018
- Zeng, Ziqi; Murugesan, Vijayakumar; Han, Kee Sung
- Nature Energy, Vol. 3, Issue 8
Stable cycling of high-voltage lithium metal batteries in ether electrolytes
journal, July 2018
- Jiao, Shuhong; Ren, Xiaodi; Cao, Ruiguo
- Nature Energy, Vol. 3, Issue 9
Stability of Solid Electrolyte Interphase Components on Lithium Metal and Reactive Anode Material Surfaces
journal, March 2016
- Leung, Kevin; Soto, Fernando; Hankins, Kie
- The Journal of Physical Chemistry C, Vol. 120, Issue 12
Effect of propylene carbonate-Li+ solvation structures on graphite exfoliation and its application in Li-ion batteries
journal, September 2017
- Shi, P. C.; Lin, M.; Zheng, H.
- Electrochimica Acta, Vol. 247
Electrochemical Scanning Tunneling Microscopy Observation of Highly Oriented Pyrolytic Graphite Surface Reactions in an Ethylene Carbonate-Based Electrolyte Solution
journal, January 1996
- Inaba, Minoru; Siroma, Zyun; Funabiki, Atsushi
- Langmuir, Vol. 12, Issue 6
Aluminum corrosion in electrolyte of Li-ion battery
journal, July 2002
- Zhang, S. S.; Jow, T. R.
- Journal of Power Sources, Vol. 109, Issue 2
A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries
journal, September 2010
- Verma, Pallavi; Maire, Pascal; Novák, Petr
- Electrochimica Acta, Vol. 55, Issue 22, p. 6332-6341
Structural and Electrochemical Properties of Li Ion Solvation Complexes in the Salt-Concentrated Electrolytes Using an Aprotic Donor Solvent, N , N -Dimethylformamide
journal, July 2016
- Fujii, Kenta; Wakamatsu, Hideaki; Todorov, Yanko
- The Journal of Physical Chemistry C, Vol. 120, Issue 31
Sacrificial Anion Reduction Mechanism for Electrochemical Stability Improvement in Highly Concentrated Li-Salt Electrolyte
journal, June 2014
- Sodeyama, Keitaro; Yamada, Yuki; Aikawa, Koharu
- The Journal of Physical Chemistry C, Vol. 118, Issue 26, p. 14091-14097
General Observation of Lithium Intercalation into Graphite in Ethylene-Carbonate-Free Superconcentrated Electrolytes
journal, March 2014
- Yamada, Yuki; Usui, Kenji; Chiang, Ching Hua
- ACS Applied Materials & Interfaces, Vol. 6, Issue 14, p. 10892-10899
In Situ Observation of Solid Electrolyte Interphase Formation in Ordered Mesoporous Hard Carbon by Small-Angle Neutron Scattering
journal, March 2012
- Bridges, Craig A.; Sun, Xiao-Guang; Zhao, Jinkui
- The Journal of Physical Chemistry C, Vol. 116, Issue 14
Correlation between Charge−Discharge Behavior of Graphite and Solvation Structure of the Lithium Ion in Propylene Carbonate-Containing Electrolytes
journal, May 2009
- Yamada, Yuki; Koyama, Yasuhiro; Abe, Takeshi
- The Journal of Physical Chemistry C, Vol. 113, Issue 20
The state of understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI) and its relationship to formation cycling
journal, August 2016
- An, Seong Jin; Li, Jianlin; Daniel, Claus
- Carbon, Vol. 105
Research Progress towards Understanding the Unique Interfaces between Concentrated Electrolytes and Electrodes for Energy Storage Applications
journal, March 2017
- Zheng, Jianming; Lochala, Joshua A.; Kwok, Alexander
- Advanced Science, Vol. 4, Issue 8
Carbon materials for lithium-ion rechargeable batteries
journal, February 1999
- Flandrois, S.; Simon, B.
- Carbon, Vol. 37, Issue 2
Mesoporous Carbon Materials: Synthesis and Modification
journal, May 2008
- Liang, Chengdu; Li, Zuojiang; Dai, Sheng
- Angewandte Chemie International Edition, Vol. 47, Issue 20, p. 3696-3717
Cycling performance and surface analysis of Lithium bis(trifluoromethanesulfonyl)imide in propylene carbonate with graphite
journal, November 2016
- Pan, Yue; Wang, Guiling; Lucht, Brett L.
- Electrochimica Acta, Vol. 217
On the correlation between surface chemistry and performance of graphite negative electrodes for Li ion batteries
journal, September 1999
- Aurbach, D.; Markovsky, B.; Weissman, I.
- Electrochimica Acta, Vol. 45, Issue 1-2
In Situ Raman Study on Electrochemical Li Intercalation into Graphite
journal, January 1995
- Inaba, Minoru
- Journal of The Electrochemical Society, Vol. 142, Issue 1
Suppression of aluminum corrosion by using high concentration LiTFSI electrolyte
journal, June 2013
- Matsumoto, Kazuaki; Inoue, Kazuhiko; Nakahara, Kentaro
- Journal of Power Sources, Vol. 231
Role of Solution Structure in Solid Electrolyte Interphase Formation on Graphite with LiPF 6 in Propylene Carbonate
journal, November 2013
- Nie, Mengyun; Abraham, Daniel P.; Seo, Daniel M.
- The Journal of Physical Chemistry C, Vol. 117, Issue 48
In situ analyses for ion storage materials
journal, January 2016
- Yang, Junghoon; Muhammad, Shoaib; Jo, Mi Ru
- Chemical Society Reviews, Vol. 45, Issue 20
Ionic liquid based lithium battery electrolytes: fundamental benefits of utilising both TFSI and FSI anions?
journal, January 2015
- Kerner, M.; Plylahan, N.; Scheers, J.
- Physical Chemistry Chemical Physics, Vol. 17, Issue 29
Filming mechanism of lithium-carbon anodes in organic and inorganic electrolytes
journal, April 1995
- Besenhard, J. O.; Winter, M.; Yang, J.
- Journal of Power Sources, Vol. 54, Issue 2
Reduction Mechanisms of Ethylene, Propylene, and Vinylethylene Carbonates
journal, January 2004
- Vollmer, James M.; Curtiss, Larry A.; Vissers, Donald R.
- Journal of The Electrochemical Society, Vol. 151, Issue 1
Correlating pore size and shape to local disorder in microporous carbon: A combined small angle neutron and X-ray scattering study
journal, October 2017
- Jafta, Charl J.; Petzold, Albrecht; Risse, Sebastian
- Carbon, Vol. 123
The Mechanisms of Lithium and Sodium Insertion in Carbon Materials
journal, January 2001
- Stevens, D. A.; Dahn, J. R.
- Journal of The Electrochemical Society, Vol. 148, Issue 8
Novel DMSO-based electrolyte for high performance rechargeable Li–O2 batteries
journal, January 2012
- Xu, Dan; Wang, Zhong-li; Xu, Ji-jing
- Chemical Communications, Vol. 48, Issue 55
Stable lithium electrodeposition in liquid and nanoporous solid electrolytes
journal, August 2014
- Lu, Yingying; Tu, Zhengyuan; Archer, Lynden A.
- Nature Materials, Vol. 13, Issue 10
In Situ Observation of Electrolyte-Concentration-Dependent Solid Electrolyte Interphase on Graphite in Dimethyl Sulfoxide
journal, April 2015
- Liu, Xing-Rui; Wang, Lin; Wan, Li-Jun
- ACS Applied Materials & Interfaces, Vol. 7, Issue 18
Structure Characterization and Lithiation Mechanism of Nongraphitized Carbon for Lithium Secondary Batteries
journal, January 2006
- Nagao, Miki; Pitteloud, Cédric; Kamiyama, Takashi
- Journal of The Electrochemical Society, Vol. 153, Issue 5
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, December 2004
- Xu, Kang
- ChemInform, Vol. 35, Issue 50
Electrolyte Solvation and Ionic Association: VI. Acetonitrile-Lithium Salt Mixtures: Highly Associated Salts Revisited
journal, January 2015
- Borodin, Oleg; Han, Sang-Don; Daubert, James S.
- Journal of The Electrochemical Society, Vol. 162, Issue 4
Corrosion Prevention Mechanism of Aluminum Metal in Superconcentrated Electrolytes
journal, October 2015
- Yamada, Yuki; Chiang, Ching Hua; Sodeyama, Keitaro
- ChemElectroChem, Vol. 2, Issue 11
Electrolyte Solvation and Ionic Association: V. Acetonitrile-Lithium Bis(fluorosulfonyl)imide (LiFSI) Mixtures
journal, January 2014
- Han, Sang-Don; Borodin, Oleg; Seo, Daniel M.
- Journal of The Electrochemical Society, Vol. 161, Issue 14
Stable Lithium Electrodeposition in Liquid and Nanoporous Solid Electrolytes
text, January 2014
- Lu, Yingying; Tu, Zhengyuan; Archer, Lynden
- arXiv
Works referencing / citing this record:
Understanding Rechargeable Battery Function Using In Operando Neutron Powder Diffraction
journal, September 2019
- Liang, Gemeng; Didier, Christophe; Guo, Zaiping
- Advanced Materials
Electrochemically induced crystallization of amorphous materials in molten MgCl 2 : boron nitride and hard carbon
journal, January 2020
- Bagri, Prashant; P. Thapaliya, Bishnu; Yang, Zhenzhen
- Chemical Communications, Vol. 56, Issue 18