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Mussa, A., Liivat, A., Marzano, F., Klett, M., Philippe, B., Tengstedt, C., . . . Svens, P. (2019). Fast-charging effects on ageing for energy-optimized automotive LiNi1/3Mn1/3Co1/3O2/graphite prismatic lithium-ion cells. Journal of Power Sources, 422, 175-184
Open this publication in new window or tab >>Fast-charging effects on ageing for energy-optimized automotive LiNi1/3Mn1/3Co1/3O2/graphite prismatic lithium-ion cells
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2019 (English)In: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 422, p. 175-184Article in journal (Refereed) Published
Abstract [en]

The reactions in energy-optimized 25 Ah prismatic NMC/graphite lithium-ion cell, as a function of fast charging (1C-4C), are more complex than earlier described. There are no clear charging rate dependent trends but rather different mechanisms dominating at the different charging rates. Ageing processes are faster at 3 and 4C charging. Cycling with 3C-charging results in accelerated lithium plating but the 4C-charging results in extensive gas evolution that contribute significantly to the large cell impedance rise. Graphite exfoliation and accelerated lithium inventory loss point to the graphite electrode as the source of the gas evolution. The results are based on careful post-mortem analyses of electrodes using: scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and electrochemical impedance spectroscopy (EIS). SEM results show particle cracking independent of the charging rate used for the cycling. XPS and EIS generally indicate thicker surface film and larger impedance, respectively, towards the edge of the jellyrolls. For the intended application of a battery electric inner-city bus using this type of cell, charging rates of 3C and above are not feasible, considering battery lifetime. However, charging rates of 2C and below are too slow from the point of view of practical charging time.

Place, publisher, year, edition, pages
ELSEVIER SCIENCE BV, 2019
Keywords
Fast charging, Lithium-ion battery, Ageing, Energy battery, Electric vehicle
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-252373 (URN)10.1016/j.jpowsour.2019.02.095 (DOI)000465365900021 ()2-s2.0-85063095386 (Scopus ID)
Note

QC 20190610

Available from: 2019-06-10 Created: 2019-06-10 Last updated: 2019-06-10Bibliographically approved
Ko, J. Y., Varini, M., Ekström, H., Klett, M. & Lindbergh, G. (2019). Porous Electrode Model with Particle Stress Effects for Li(Ni1/3Co1/3Mn1/3)O2 Electrode. Journal of the Electrochemical Society
Open this publication in new window or tab >>Porous Electrode Model with Particle Stress Effects for Li(Ni1/3Co1/3Mn1/3)O2 Electrode
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2019 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111Article in journal (Refereed) Published
Abstract [en]

A porous electrode model, incorporating particle stress effects, is developed for the electrode kinetic processes in the positive Li(Ni1/3Mn1/3Co1/3)O2 or NMC111 electrode. The model is used to analyze experimental data from galvanostatic intermittent titration technique (GITT) during charging at the beginning of life. The equilibrium potential accounts for the influence of mechanical stress in the electrode particles. While the standard Newman-based model proves unable to capture the dynamic performance of NMC111, the extended model with stress allows good fits of the GITT responses for NMC half cells for a voltage range from 3.7–4.1 V vs Li/Li+ at 10°C, 25°C and 40°C. Four physical parameters are extracted to analyze the underlying diffusive, kinetic, thermodynamic and stress phenomena from polarization to relaxation during a GITT transient. Strong dependencies of the kinetic rate constant k, slope of the open-circuit potential curve dEconc/dxpos and stress proportionality factor ϒstress with lithium concentration are found. The effective diffusion coefficients Ds,eff are ∼10−14 – 10−13 cm2/s across voltages and temperatures. Diffusion limitation and particle surface stress are more profound at higher voltages and at higher temperatures. This leads to large lithium concentration gradient near particle surface, requiring longer relaxation time during GITT.

Keywords
Batteries - Lithium, Electrode Kinetics
National Category
Engineering and Technology
Identifiers
urn:nbn:se:kth:diva-256548 (URN)10.1149/2.0661913jes (DOI)000483501000003 ()
Note

QC 20190903

Available from: 2019-08-28 Created: 2019-08-28 Last updated: 2019-09-27Bibliographically approved
Mussa, A. S., Klett, M., Lindbergh, G. & Wreland Lindström, R. (2018). Effects of external pressure on the performance and ageing of single-layer lithium-ion pouch cells. Journal of Power Sources, 385, 18-26
Open this publication in new window or tab >>Effects of external pressure on the performance and ageing of single-layer lithium-ion pouch cells
2018 (English)In: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 385, p. 18-26Article in journal (Refereed) Published
Abstract [en]

The effects of external compression on the performance and ageing of NMC(1/3)/Graphite single-layer Li-ion pouch cells are investigated using a spring-loaded fixture. The influence of pressure (0.66, 0.99, 1.32, and 1.98 MPa) on impedance is characterized in fresh cells that are subsequently cycled at the given pressure levels. The aged cells are analyzed for capacity fade and impedance rise at the cell and electrode level. The effect of pressure distribution that may occur in large-format cells or in a battery pack is simulated using parallel connected cells. The results show that the kinetic and mass transport resistance increases with pressure in a fresh cell. An optimum pressure around 1.3 MPa is shown to be beneficial to reduce cyclable-lithium loss during cycling. The minor active mass losses observed in the electrodes are independent of the ageing pressure, whereas ageing pressure affects the charge transfer resistance of both NMC and graphite electrodes and the ohmic resistance of the cell. Pressure distribution induces current distribution but the enhanced current throughput at lower pressures cell does not accelerate its ageing. Conclusions from this work can explain some of the discrepancies in non-uniform ageing reported in the literature and indicate coupling between electrochemistry and mechanics.

Place, publisher, year, edition, pages
Elsevier, 2018
Keywords
Current distribution, Lithium-ion battery, Mechanics, Non-uniform ageing, Pressure
National Category
Other Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-224547 (URN)10.1016/j.jpowsour.2018.03.020 (DOI)000430779400003 ()2-s2.0-85043458948 (Scopus ID)
Funder
Swedish Energy Agency, 30770-3StandUp
Note

QC 20180321

Available from: 2018-03-21 Created: 2018-03-21 Last updated: 2018-07-23Bibliographically approved
Mussa, A., Lindbergh, G., Klett, M., Gudmundson, P., Svens, P. & Lindström, R. (2018). Inhomogeneous active layer contact loss in a cycled prismatic lithium-ion cell caused by the jelly-roll curvature. Journal of Energy Storage, 20, 213-217
Open this publication in new window or tab >>Inhomogeneous active layer contact loss in a cycled prismatic lithium-ion cell caused by the jelly-roll curvature
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2018 (English)In: Journal of Energy Storage, E-ISSN 2352-152X, Vol. 20, p. 213-217Article in journal (Refereed) Published
Abstract [en]

Internal resistance is a key parameter that affects the power, energy, efficiency, lifetime, and safety of a lithium-ion battery. It grows due to chemical and mechanical battery wear during ageing. In this work, the effect of the jelly-roll winding curvature on impedance rise is investigated. NMC electrode samples, harvested from the curved as well as the flat regions of the jelly-roll from cycle-aged and calendar-aged prismatic cells (25 Ah, hard casing) are investigated by electrochemical impedance spectroscopy. After cycling, larger impedance rise is observed at the outer radius (concave) of the curved region compared to the inner radius (convex) or the flat region of the jelly-roll, and the difference increases with a decrease in the jelly-roll radius of curvature, from the cell skin towards the core. To identify the causes behind the observed difference in the impedance rise, investigations at different external compression (0 and 2.5 MPa) and temperature (5 and 25 °C) are performed. The results show that contact loss between the current collector and the active layer is the main source of the difference in impedance rise. Mechanical mechanisms that may cause the contact loss are discussed and design recommendations to mitigate the rise in impedance are given. 

Place, publisher, year, edition, pages
Elsevier Ltd, 2018
Keywords
Bending stress, Contact loss, Curvature, Diffusion induced stress (DIS), Lithium-ion battery, Mechanical ageing, Electrochemical impedance spectroscopy, Ions, Stresses, Diffusion induced stresses (DIS), Lithium-ion batteries
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-236555 (URN)10.1016/j.est.2018.09.012 (DOI)000451147100021 ()2-s2.0-85054131101 (Scopus ID)
Funder
Swedish Energy Agency, 30770-3
Note

Funding text: This work was supported by the Swedish Energy Agency ( 30770-3 ) under the program Energy Efficient Vehicles, the StandUp for Energy, the Battery Fund Program, and Swedish Electromobility Centre. Dr. Fernanda Marzano (Scania CV AB) is acknowledged for helping with the cell opening. Appendix A. QC 20181127

Available from: 2018-11-27 Created: 2018-11-27 Last updated: 2018-12-11Bibliographically approved
Mussa, A. S., Klett, M., Behm, M., Lindbergh, G. & Lindström, R. W. (2017). Fast-charging to a partial state of charge in lithium-ion batteries: A comparative ageing study. Journal of Energy Storage, 13, 325-333
Open this publication in new window or tab >>Fast-charging to a partial state of charge in lithium-ion batteries: A comparative ageing study
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2017 (English)In: Journal of Energy Storage, ISSN 2352-152X, Vol. 13, p. 325-333Article in journal (Refereed) Published
Abstract [en]

At electric vehicle fast-charging stations, it is generally recommended to avoid charging beyond similar to 80% State-of-Charge (SOC) since topping-off to full capacity disproportionately increases the charging time. This necessitates studying its long-term impact compared to slower rate charging to full capacity typical of home or residential charging. Here we present the long-term ageing effects on commercial 18650 NMC-LMO/graphite cell cycled between 2.6-4.2 V at three different charging protocols: 1.5 C-rate fast-partial charging ( to 82.5% SOC), 0.5 C-rate slow standard charging without or with a constant-voltage step (to 93% or 100% SOC). Quantitative discharge-curve and postmortem analyses are used to evaluate ageing. The results show that ageing rate increases in the order: fast-partial charging < standard charging < standard charging with constant-voltage period, indicating that higher SOC-range near full capacity is more detrimental to battery life than fast-charging. The capacity fade is totally dominated by cyclable-lithium loss. The similar to 8% NMC-LMO active material loss has negligible impact on the cell capacity fade due to the electrodes excess material in the fresh cell and its moderate loss rate with ageing compared to the cyclable-lithium. Similar ageing modes in terms of capacity fade and impedance rise are found irrespective of the charging protocol.

Place, publisher, year, edition, pages
Elsevier, 2017
Keywords
Fast-charging, Charging to partial SOC, Non-destructive analysis, Lithium-ion battery ageing, Battery management, Charging protocol
National Category
Energy Engineering
Identifiers
urn:nbn:se:kth:diva-220495 (URN)10.1016/j.est.2017.07.004 (DOI)000417183300033 ()2-s2.0-85028014032 (Scopus ID)
Funder
Swedish Energy AgencyStandUp
Note

QC 20171222

Available from: 2017-12-22 Created: 2017-12-22 Last updated: 2018-04-24Bibliographically approved
Klett, M., Svens, P., Tengstedt, C., Seyeux, A., Swiatowska, J., Lindbergh, G. & Wreland Lindström, R. (2015). Uneven Film Formation across Depth of Porous Graphite Electrodes in Cycled Commercial Li-Ion Batteries. The Journal of Physical Chemistry C, 119(1), 90-100
Open this publication in new window or tab >>Uneven Film Formation across Depth of Porous Graphite Electrodes in Cycled Commercial Li-Ion Batteries
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2015 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 1, p. 90-100Article in journal (Refereed) Published
Abstract [en]

A critical aging mechanism in lithium-ion batteries is the decomposition of the electrolyte at the negative electrode forming a solid electrolyte interphase (SEI) layer that increases impedance and consumes cyclable lithium. In contrast to the typical nanometer SEI layer generally discussed, this paper reports on the formation of a micrometer thick film on top of and within the upper part of a porous graphite electrode in a deep-cycled commercial cylindrical LiFePO4/graphite cell. Morphological, chemical, and electrochemical characterizations were performed by means of cross-sectional electron microscopy in combination with energy dispersive X-ray spectroscopy and focused ion-beam milling, time-of-flight secondary ion mass spectrometry, and electrochemical impedance spectroscopy (EIS) to evaluate the properties and impact of the uneven film. It is shown that the film is enriched in PO and carbonate species but is otherwise similar in composition to the thin SEI formed on a calendar-aged electrode and clogs the pores in the electrode closest to the separator. Performance evaluation by physics-based EIS modeling supports a local porosity decrease, impeding the effective electrolyte transport in the electrode. The local variation of electrode properties implies that current distribution in the porous electrode under these cycling conditions causes inefficient material utilization and sustained uneven electrode degradation.

Keywords
Capacity Fade, Impedance Spectroscopy, Postmortem Analysis, Thin-Film, Tof-Sims, Electrochemical Characterization, Photoelectron-Spectroscopy, Lithium Intercalation, Mass-Spectrometry, Aging Mechanisms
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:kth:diva-160750 (URN)10.1021/jp509665e (DOI)000347744700012 ()2-s2.0-84920651710 (Scopus ID)
Funder
Swedish Energy Agency
Note

QC 20150302

Available from: 2015-03-02 Created: 2015-02-27 Last updated: 2017-12-04Bibliographically approved
Klett, M., Zavalis, T., Hellqvist Kjell, M., Wreland Lindström, R., Behm, M. & Lindbergh, G. (2014). Altered electrode degradation with temperature in LiFePO4/mesocarbon microbead graphite cells diagnosed with impedance spectroscopy. Electrochimica Acta, 141, 173-181
Open this publication in new window or tab >>Altered electrode degradation with temperature in LiFePO4/mesocarbon microbead graphite cells diagnosed with impedance spectroscopy
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2014 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 141, p. 173-181Article in journal (Other academic) Published
Abstract [en]

Electrode degradation in LiFePO4 / mesocarbon microbead graphite (MCMB) pouch cells aged at 55 °C by a synthetic hybrid drive cycle or storage is diagnosed and put into context with previous results of aging at 22 °C. The electrode degradation is evaluated by means of electrochemical impedance spectroscopy (EIS), measured separately on electrodes harvested from the cells, and by using a physics-based impedance model for aging evaluation. Additional capacity measurements, scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX) are used in the evaluation. At 55 °C the LiFePO4 electrode shows increased particle/electronic conductor resistance, for both stored and cycled electrodes. This differs from results obtained at 22 °C, where the electrode suffered lowered porosity, particle fracture, and loss of active material. For graphite, only cycling gave a sustained effect on electrode performance at 55 °C due to lowered porosity and changes of surface properties, and to greater extent than at low temperature. Furthermore, increased current collector resistance also contributes to a large part of the pouch cell impedance when aged at increased temperatures. The result shows that increased temperature promotes different degradation on the electrode level, and is an important implication for high temperature accelerated aging. In light of the electrode observations, the correlation between full-cell and electrode impedances is discussed.

Keywords
battery aging;temperature;electrode impedance;EIS modeling;LiFePO4/MCMB graphite
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-145053 (URN)10.1016/j.electacta.2014.06.081 (DOI)000343022900023 ()2-s2.0-84905868311 (Scopus ID)
Funder
Swedish Energy Agency
Note

Updated from "Manuscript" to "Journal". QC 20141112

Available from: 2014-05-07 Created: 2014-05-07 Last updated: 2017-12-05Bibliographically approved
Klett, M. (2014). Electrochemical Studies of Aging in Lithium-Ion Batteries. (Doctoral dissertation). Stockholm: KTH Royal Institute of Technology
Open this publication in new window or tab >>Electrochemical Studies of Aging in Lithium-Ion Batteries
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Lithium-ion batteries are today finding use in automobiles aiming at reducing fuel consumption and emissions within transportation. The requirements on batteries used in vehicles are high regarding performance and lifetime, and a better understanding of the interior processes that dictate energy and power capabilities is a key to strategic development. This thesis concerns aging in lithium-ion cells using electrochemical tools to characterize electrode and electrolyte properties that affect performance and performance loss in the cells.

 

A central difficulty regarding battery aging is to manage the coupled effects of temperature and cycling conditions on the various degradation processes that determine the lifetime of a cell. In this thesis, post-mortem analyses on harvested electrode samples from small pouch cells and larger cylindrical cells aged under different conditions form the basis of aging evaluation. The characterization is focused on electrochemical impedance spectroscopy (EIS) measurements and physics-based EIS modeling supported by several material characterization techniques to investigate degradation in terms of properties that directly affect performance. The results suggest that increased temperature alter electrode degradation and limitations relate in several cases to electrolyte transport. Variations in electrode properties sampled from different locations in the cylindrical cells show that temperature and current distributions from cycling cause uneven material utilization and aging, in several dimensions. The correlation between cell performance and localized utilization/degradation is an important aspect in meeting the challenges of battery aging in vehicle applications.

 

The use of in-situ nuclear magnetic resonance (NMR) imaging to directly capture the development of concentration gradients in a battery electrolyte during operation is successfully demonstrated. The salt diffusion coefficient and transport number for a sample electrolyte are obtained from Li+ concentration profiles using a physics-based mass-transport model. The method allows visualization of performance limitations and can be a useful tool in the study of electrochemical systems.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2014. p. x, 72
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2014:16
Keywords
aging, EIS modeling, electrolyte characterization, graphite, hybrid electric vehicles, impedance spectroscopy, LiFePO4, Li-ion batteries
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-145057 (URN)978-91-7595-116-4 (ISBN)
Public defence
2014-05-28, Sal F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Swedish Energy Agency
Note

QC 20140512

Available from: 2014-05-12 Created: 2014-05-07 Last updated: 2017-02-22Bibliographically approved
Klett, M., Eriksson, R., Groot, J., Svens, P., Ciosek Högström, K., Wreland Lindström, R., . . . Edström, K. (2014). Non-uniform aging of cycled commercial LiFePO4//graphite cylindrical cells revealed by post-mortem analysis. Journal of Power Sources, 257, 126-137
Open this publication in new window or tab >>Non-uniform aging of cycled commercial LiFePO4//graphite cylindrical cells revealed by post-mortem analysis
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2014 (English)In: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 257, p. 126-137Article in journal (Refereed) Published
Abstract [en]

Aging of power-optimized commercial 2.3 Ah cylindrical LiFePO4//graphite cells to be used in hybrid electric vehicle is investigated and compared for three different aging procedures; (i) using a simulated hybrid electric vehicle cycle within a narrow SOC-range, (ii) using a constant-current cycle over a 100% SOC-range, and (iii) stored during three years at 22 degrees C. Postmortem analysis of the cells is performed after full-cell electrochemical characterization and discharge. EIS and capacity measurements are made on different parts of the disassembled cells. Material characterization includes SEM, EDX, HAXPES/XPS and XRD. The most remarkable result is that both cycled cells displayed highly uneven aging primarily of the graphite electrodes, showing large differences between the central parts of the jellyroll compared to the outer parts. The aging variations are identified as differences in capacity and impedance of the graphite electrode, associated with different SEI characteristics. Loss of cyclable lithium is mirrored by a varying degree of lithiation in the positive electrode and electrode slippage. The spatial variation in negative electrode degradation and utilization observed is most likely connected to gradients in temperature and pressure, that can give rise to current density and potential distributions within the jellyroll during cycling.

Keywords
Battery aging, LiFePO4/graphite cells, Hybrid electric vehicle, Synchrotron material characterization, Electrode utilization
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-145047 (URN)10.1016/j.jpowsour.2014.01.105 (DOI)000333780000017 ()2-s2.0-84894504735 (Scopus ID)
Funder
Swedish Energy Agency
Note

QC 20140509

Available from: 2014-05-07 Created: 2014-05-07 Last updated: 2017-12-05Bibliographically approved
Zavalis, T. G., Klett, M., Kjell, M., Behm, M., Wreland Lindström, R. & Lindbergh, G. (2013). Aging in Lithium-Ion Batteries: Experimental and Model Investigation of Harvested LiFePO4 and Mesocarbon Microbead Graphite Electrodes. Electrochimica Acta, 110, 335-348
Open this publication in new window or tab >>Aging in Lithium-Ion Batteries: Experimental and Model Investigation of Harvested LiFePO4 and Mesocarbon Microbead Graphite Electrodes
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2013 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 110, p. 335-348Article in journal (Refereed) Published
Abstract [en]

This study investigates aging in LiFePO4/mesocarbon microbead graphite cells that have been subjected to either a synthetic hybrid drive cycle or calendar aging, at 22 C. The investigation involves detailed examination and comparison of harvested fresh and aged electrodes. The electrode properties are determined using a physics-based electrochemical impedance spectroscopy (EIS) model that is fitted to three-electrode EIS measurements, with input from measured electrode capacity and scanning electrode microscopy (SEM). Results from the model fitting provide a detailed insight to the electrode degradation and is put into context with the behavior of the full cell aging. It was established that calendar aging has negligible effect on cell impedance, while cycle aging increases the impedance mainly due to structural changes in the LiFePO4 porous electrode and electrolyte decomposition products on both electrodes. Further, full-cell capacity fade is mainly a consequence of cyclable lithium loss caused by electrolyte decomposition.

Keywords
Lithium-ion battery, Aging, EIS modeling, LiFePO4, Graphite
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-122395 (URN)10.1016/j.electacta.2013.05.081 (DOI)000329530300044 ()2-s2.0-84888320795 (Scopus ID)
Funder
StandUpSwedish Energy Agency
Note

 QC 20140120. Updated from "Accepted" to "Published".

Available from: 2013-05-20 Created: 2013-05-20 Last updated: 2017-12-06Bibliographically approved
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0003-4901-5820

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