Measuring Li+ inventory losses in LiCoO2/graphite cells using Raman microscopy

Snyder, Chelsea Marie; Apblett, Christopher A.; Grillet, Anne; Duquette, David

doi:10.1149/2.1111606jes

Title: Measuring Li⁺ inventory losses in LiCoO₂/graphite cells using Raman microscopy

Abstract

Here, the contribution from loss of Li⁺ inventory to capacity fade is described for slow rates (C/10) and long-term cycling (up to 80 cycles). It was found through electrochemical testing and ex-situ Raman analysis that at these slow rates, the entirety of capacity loss up to 80 cycles can be explained by loss of Li⁺ inventory in the cell. The Raman spectrum of LiCoO₂ is sensitive to the state of lithiation and can therefore be leveraged to quantify the state of lithiation for individual particles. With these Raman derived estimates, the lithiation state of the cathode in the discharged state is compared to electrochemical data as a function of cycle number. High correlation is found between Raman quantifications of cycleable lithium and the capacity fade. Additionally, the linear relationship between discharge capacity and cell overpotential suggests that the loss of capacity stems from an impedance rise of the electrodes, which based on Li inventory losses, is caused by SEI formation and repair.

Authors:

Snyder, Chelsea Marie ^[1]; Apblett, Christopher A. ^[2]; Grillet, Anne ^[2]; Thomas Edwin Beechem; Duquette, David ^[3]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Rensselaer Polytechnic Institute, Troy, NY (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Rensselaer Polytechnic Institute, Troy, NY (United States)

Publication Date:: Fri Mar 25 00:00:00 EDT 2016

Research Org.:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1247658

Report Number(s):: SAND-2016-0211J
Journal ID: ISSN 0013-4651; 618347

Grant/Contract Number:: AC04-94AL85000

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the Electrochemical Society

Additional Journal Information:: Journal Volume: 163; Journal Issue: 6; Journal ID: ISSN 0013-4651

Publisher:: The Electrochemical Society

Country of Publication:: United States

Language:: English

Subject:: 25 ENERGY STORAGE; 36 MATERIALS SCIENCE; capacity loss; LiCoO₂; lithium ion batteries; Raman

Citation Formats


                    Snyder, Chelsea Marie, Apblett, Christopher A., Grillet, Anne, Thomas Edwin Beechem, and Duquette, David. Measuring Li+ inventory losses in LiCoO2/graphite cells using Raman microscopy.  United States: N. p., 2016. 
Web.  doi:10.1149/2.1111606jes.

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                    Snyder, Chelsea Marie, Apblett, Christopher A., Grillet, Anne, Thomas Edwin Beechem, & Duquette, David. Measuring Li+ inventory losses in LiCoO2/graphite cells using Raman microscopy.  United States.  https://doi.org/10.1149/2.1111606jes

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                    Snyder, Chelsea Marie, Apblett, Christopher A., Grillet, Anne, Thomas Edwin Beechem, and Duquette, David. Fri .  
"Measuring Li+ inventory losses in LiCoO2/graphite cells using Raman microscopy".  United States.  https://doi.org/10.1149/2.1111606jes.  https://www.osti.gov/servlets/purl/1247658.

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@article{osti_1247658,

  title        = {Measuring Li+ inventory losses in LiCoO2/graphite cells using Raman microscopy},

  author       = {Snyder, Chelsea Marie and Apblett, Christopher A. and Grillet, Anne and Thomas Edwin Beechem and Duquette, David},

  abstractNote = {Here, the contribution from loss of Li+ inventory to capacity fade is described for slow rates (C/10) and long-term cycling (up to 80 cycles). It was found through electrochemical testing and ex-situ Raman analysis that at these slow rates, the entirety of capacity loss up to 80 cycles can be explained by loss of Li+ inventory in the cell. The Raman spectrum of LiCoO2 is sensitive to the state of lithiation and can therefore be leveraged to quantify the state of lithiation for individual particles. With these Raman derived estimates, the lithiation state of the cathode in the discharged state is compared to electrochemical data as a function of cycle number. High correlation is found between Raman quantifications of cycleable lithium and the capacity fade. Additionally, the linear relationship between discharge capacity and cell overpotential suggests that the loss of capacity stems from an impedance rise of the electrodes, which based on Li inventory losses, is caused by SEI formation and repair.},

  doi          = {10.1149/2.1111606jes},

  journal      = {Journal of the Electrochemical Society},

  number       = 6,

  volume       = 163,

  place        = {United States},

  year         = {Fri Mar 25 00:00:00 EDT 2016},

  month        = {Fri Mar 25 00:00:00 EDT 2016}

}

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Works referenced in this record:

Recent developments in lithium ion batteries
journal, June 2001

Wakihara, Masataka
Materials Science and Engineering: R: Reports, Vol. 33, Issue 4
DOI: 10.1016/S0927-796X(01)00030-4

Main aging mechanisms in Li ion batteries
journal, August 2005

Broussely, M.; Biensan, Ph.; Bonhomme, F.
Journal of Power Sources, Vol. 146, Issue 1-2
DOI: 10.1016/j.jpowsour.2005.03.172

Capacity fade study of lithium-ion batteries cycled at high discharge rates
journal, May 2003

Ning, Gang; Haran, Bala; Popov, Branko N.
Journal of Power Sources, Vol. 117, Issue 1-2
DOI: 10.1016/S0378-7753(03)00029-6

Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: Methodology, insights and novel approaches
journal, February 2015

Hausbrand, R.; Cherkashinin, G.; Ehrenberg, H.
Materials Science and Engineering: B, Vol. 192
DOI: 10.1016/j.mseb.2014.11.014

Real-time stress measurements in lithium-ion battery negative-electrodes
journal, May 2012

Sethuraman, V. A.; Van Winkle, N.; Abraham, D. P.
Journal of Power Sources, Vol. 206, p. 334-342
DOI: 10.1016/j.jpowsour.2012.01.036

Threefold Increase in the Young’s Modulus of Graphite Negative Electrode during Lithium Intercalation
journal, January 2010

Qi, Yue; Guo, Haibo; Hector, Louis G.
Journal of The Electrochemical Society, Vol. 157, Issue 5
DOI: 10.1149/1.3327913

CoO₂, The End Member of the Li_xCoO₂ Solid Solution
journal, January 1996

Amatucci, G. G.; Tarascon, J. M.; Klein, L. C.
Journal of The Electrochemical Society, Vol. 143, Issue 3, p. 1114-1123
DOI: 10.1149/1.1836594

Aging of a Commercial Graphite/LiFePO4 Cell
journal, January 2011

Safari, M.; Delacourt, C.
Journal of The Electrochemical Society, Vol. 158, Issue 10
DOI: 10.1149/1.3614529

Electrochemical characterization and post-mortem analysis of aged LiMn2O4–NMC/graphite lithium ion batteries part II: Calendar aging
journal, July 2014

Stiaszny, Barbara; Ziegler, Jörg C.; Krauß, Elke E.
Journal of Power Sources, Vol. 258
DOI: 10.1016/j.jpowsour.2014.02.019

Stress evolution and capacity fade in constrained lithium-ion pouch cells
journal, January 2014

Cannarella, John; Arnold, Craig B.
Journal of Power Sources, Vol. 245
DOI: 10.1016/j.jpowsour.2013.06.165

Raman diagnostics of LiCoO2 electrodes for lithium-ion batteries
journal, June 2014

Gross, Toni; Hess, Christian
Journal of Power Sources, Vol. 256
DOI: 10.1016/j.jpowsour.2014.01.084

Visualization of the State-of-Charge Distribution in a LiCoO ₂ Cathode by In Situ Raman Imaging
journal, January 2013

Nishi, Toshio; Nakai, Hideki; Kita, Akinori
Journal of The Electrochemical Society, Vol. 160, Issue 10
DOI: 10.1149/2.061310jes

Influence of the PVdF binder on the stability of LiCoO2 electrodes
journal, December 2005

Markevich, E.; Salitra, G.; Aurbach, D.
Electrochemistry Communications, Vol. 7, Issue 12
DOI: 10.1016/j.elecom.2005.09.010

In Situ Raman Microscopy of Individual LiNi _0.8 Co _0.15 Al _0.05 O ₂ Particles in a Li-Ion Battery Composite Cathode
journal, January 2005

Lei, Jinglei; McLarnon, Frank; Kostecki, Robert
The Journal of Physical Chemistry B, Vol. 109, Issue 2
DOI: 10.1021/jp046027c

Advanced in situ methods for the characterization of practical electrodes in lithium-ion batteries
journal, September 2000

Novák, P.; Panitz, J. -C.; Joho, F.
Journal of Power Sources, Vol. 90, Issue 1
DOI: 10.1016/S0378-7753(00)00447-X

The Li-Ion Rechargeable Battery: A Perspective
journal, January 2013

Goodenough, John B.; Park, Kyu-Sung
Journal of the American Chemical Society, Vol. 135, Issue 4
DOI: 10.1021/ja3091438

Electronic structure and lattice dynamics of Li _x CoO ₂ single crystals
journal, September 2015

Liu, H. L.; Ou-Yang, T. Y.; Tsai, H. H.
New Journal of Physics, Vol. 17, Issue 10
DOI: 10.1088/1367-2630/17/10/103004

Effect of pressure on the structural properties and Raman modes of ${LiCoO}_{2}$
journal, December 2005

Wang, X.; Loa, I.; Kunc, K.
Physical Review B, Vol. 72, Issue 22
DOI: 10.1103/PhysRevB.72.224102

Weighting hyperspectral image data for improved multivariate curve resolution results
journal, September 2008

Jones, Howland D. T.; Haaland, David M.; Sinclair, Michael B.
Journal of Chemometrics, Vol. 22, Issue 9, p. 482-490
DOI: 10.1002/cem.1170

The role of particle size in cathode optimization in alkaline primary batteries
journal, January 2001

Urfer, A.; Lawrance, G. A.; Swinkels, D. A. J.
Journal of Applied Electrochemistry, Vol. 31, Issue 3, p. 341-347
DOI: 10.1023/A:1017512721635

Works referencing / citing this record:

Ex situ and operando study of LiCoO ₂ thin films by Raman spectroscopy: Thermal and electrochemical properties
journal, July 2019

Le Van‐Jodin, Lucie; Rouchon, Denis; Le, Van‐Hoan
Journal of Raman Spectroscopy, Vol. 50, Issue 10
DOI: 10.1002/jrs.5669

Electrochemical Cycle-Life Characterization of High Energy Lithium-Ion Cells with Thick Li(Ni _0.6 Mn _0.2 Co _0.2 )O ₂ and Graphite Electrodes
journal, January 2017

Leng, Yongjun; Ge, Shanhai; Marple, Dan
Journal of The Electrochemical Society, Vol. 164, Issue 6
DOI: 10.1149/2.0451706jes

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Similar Records

Title: Measuring Li+ inventory losses in LiCoO2/graphite cells using Raman microscopy

Abstract

Citation Formats

Recent developments in lithium ion batteries journal, June 2001

Main aging mechanisms in Li ion batteries journal, August 2005

Capacity fade study of lithium-ion batteries cycled at high discharge rates journal, May 2003

Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: Methodology, insights and novel approaches journal, February 2015

Real-time stress measurements in lithium-ion battery negative-electrodes journal, May 2012

Threefold Increase in the Young’s Modulus of Graphite Negative Electrode during Lithium Intercalation journal, January 2010

CoO2, The End Member of the LixCoO2 Solid Solution journal, January 1996

Aging of a Commercial Graphite/LiFePO4 Cell journal, January 2011

Electrochemical characterization and post-mortem analysis of aged LiMn2O4–NMC/graphite lithium ion batteries part II: Calendar aging journal, July 2014

Stress evolution and capacity fade in constrained lithium-ion pouch cells journal, January 2014

Raman diagnostics of LiCoO2 electrodes for lithium-ion batteries journal, June 2014

Visualization of the State-of-Charge Distribution in a LiCoO 2 Cathode by In Situ Raman Imaging journal, January 2013

Influence of the PVdF binder on the stability of LiCoO2 electrodes journal, December 2005

In Situ Raman Microscopy of Individual LiNi 0.8 Co 0.15 Al 0.05 O 2 Particles in a Li-Ion Battery Composite Cathode journal, January 2005

Advanced in situ methods for the characterization of practical electrodes in lithium-ion batteries journal, September 2000

The Li-Ion Rechargeable Battery: A Perspective journal, January 2013

Electronic structure and lattice dynamics of Li x CoO 2 single crystals journal, September 2015

Effect of pressure on the structural properties and Raman modes of LiCoO 2 journal, December 2005

Weighting hyperspectral image data for improved multivariate curve resolution results journal, September 2008

The role of particle size in cathode optimization in alkaline primary batteries journal, January 2001

Ex situ and operando study of LiCoO 2 thin films by Raman spectroscopy: Thermal and electrochemical properties journal, July 2019

Electrochemical Cycle-Life Characterization of High Energy Lithium-Ion Cells with Thick Li(Ni 0.6 Mn 0.2 Co 0.2 )O 2 and Graphite Electrodes journal, January 2017

Title: Measuring Li⁺ inventory losses in LiCoO₂/graphite cells using Raman microscopy

Recent developments in lithium ion batteries
journal, June 2001

Main aging mechanisms in Li ion batteries
journal, August 2005

Capacity fade study of lithium-ion batteries cycled at high discharge rates
journal, May 2003

Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: Methodology, insights and novel approaches
journal, February 2015

Real-time stress measurements in lithium-ion battery negative-electrodes
journal, May 2012

Threefold Increase in the Young’s Modulus of Graphite Negative Electrode during Lithium Intercalation
journal, January 2010

CoO₂, The End Member of the Li_xCoO₂ Solid Solution
journal, January 1996

Aging of a Commercial Graphite/LiFePO4 Cell
journal, January 2011

Electrochemical characterization and post-mortem analysis of aged LiMn2O4–NMC/graphite lithium ion batteries part II: Calendar aging
journal, July 2014

Stress evolution and capacity fade in constrained lithium-ion pouch cells
journal, January 2014

Raman diagnostics of LiCoO2 electrodes for lithium-ion batteries
journal, June 2014

Visualization of the State-of-Charge Distribution in a LiCoO ₂ Cathode by In Situ Raman Imaging
journal, January 2013

Influence of the PVdF binder on the stability of LiCoO2 electrodes
journal, December 2005

In Situ Raman Microscopy of Individual LiNi _0.8 Co _0.15 Al _0.05 O ₂ Particles in a Li-Ion Battery Composite Cathode
journal, January 2005

Advanced in situ methods for the characterization of practical electrodes in lithium-ion batteries
journal, September 2000

The Li-Ion Rechargeable Battery: A Perspective
journal, January 2013

Electronic structure and lattice dynamics of Li _x CoO ₂ single crystals
journal, September 2015

Effect of pressure on the structural properties and Raman modes of ${LiCoO}_{2}$
journal, December 2005

Weighting hyperspectral image data for improved multivariate curve resolution results
journal, September 2008

The role of particle size in cathode optimization in alkaline primary batteries
journal, January 2001

Ex situ and operando study of LiCoO ₂ thin films by Raman spectroscopy: Thermal and electrochemical properties
journal, July 2019

Electrochemical Cycle-Life Characterization of High Energy Lithium-Ion Cells with Thick Li(Ni _0.6 Mn _0.2 Co _0.2 )O ₂ and Graphite Electrodes
journal, January 2017