Operando lithium plating quantification and early detection of a commercial LiFePO4 cell cycled under dynamic driving schedule

Significance Statement

The increase in cycle life requirements and duty-loads in electric vehicles along with battery energy storage systems have continued to put pressure on the search for precise and reliable battery control systems. Battery management systems are control systems composed of hardware as well as software that are made to ensure proper operation of lithium ion batteries. Despite the huge steps that have been made in the enhancement of the battery management systems technology, detrimental battery failures are still being recorded.

Lithium plating has been identified as the most detrimental occurrence in lithium ion batteries. It results in dendrite induced short-circuiting. This has led to massive losses, which affects battery industry and manufacturers’ reputation. It also poses a major safety concern to the battery users. Therefore, it is important to improve further battery monitoring. Advanced method to operando diagnose and predict battery degradation mechanisms and lithium-plating development will form the basis of these developments. This will be a challenging task, but will be a significant step towards battery monitoring.

Reference to the effects of lithium plating on the performance of lithium ion batteries as well as users’ safety, a lot of efforts have been put in trying to elucidate its effects further and to come up with its detection methods.

David Anseán, V.M. García, J.C. Viera, and M. González at University of Oviedo in Spain in collaboration with Matthieu Dubarry, A. Devie, B.Y. Liaw at University of Hawai’i demonstrated an analysis to operando identify and quantify lithium plating on graphite LiFePO4 cell. They tested the cell at ambient temperature implementing standard dynamic stress test driving schedule. They implemented a framework that merged both electrochemical and computer simulation methods. Incremental capacity evaluation was used to establish and trace reversible lithium plating and uncover the causes of cell degradation. Their research work is published in Journal of Power Sources.

The research team coupled the evaluation of the peak area and incremental capacity to establish and quantify the presence of a new phase transformation in the cell voltage signature. The phase occurred from the reversible lithium-plating occurrence. The researchers then analyzed the nature of lithium plating origin and observed that gradual degradation caused the cell to plate. The mechanistic model simulations allowed for operando identification of the ongoing aging modes, estimation of the reversible amount of lithium plating, and projection of half-cell degradation on both electrodes throughout the cycling.

The outcomes indicated that large loss of active material on delithiated negative electrode caused cell imbalance eventually. This resulted to overlithiate the negative electrode and subsequently induced lithium plating. Quantitative analysis also highlighted the effects of lithium plating. The loss of lithium inventory was raised by a factor of 4. The results of this study indicated the importance of tracking cell-aging mechanisms to predict, uncover and estimate lithium plating.

The researchers demonstrated that early detection of lithium plating comes with some benefits. First, it can be implemented in battery systems to curtail the duty-cycling scheme requirements, therefore, helps avoid further degradation and prolongs cycle-life. This straightforward, in situ, and cost effective method can be used to enhance battery management system functions for prognosis and diagnosis.

Their study also focused on the potential of the alawa toolbox  developed by Matthieu Dubarry at University of Hawai’i, to forecast the impact of none only the main degradation mechanisms but also the reversible and irreversible parts of lithium plating. This framework can be helpful to researchers focusing on the correlation of the cell design parameters with normal battery degradation, such as loss of lithium inventory and loss of active material as well as abnormal degradation such as lithium plating occurrence.

Operando lithium plating quantification and early detection of a commercial LiFePO4 cell cycled under dynamic driving schedule. Advances in Engineering

About the author

David Anseán, PhD
Assistant Professor
Department of Electrical Engineering
University of Oviedo
Polytechnic School of Engineering, 33204, Gijón, Spain
Email: [email protected]

David Anseán is an Assistant Professor at the University of Oviedo, where he carries out his research activities in the Battery Research Laboratory. His research focuses on lithium ion battery degradation mechanisms detection and analysis via noninvasive methods, battery testing and characterization, and design and implementation of battery fast charging techniques.

He obtained his M.S. degree from the University of Granada (Spain) in 2007, and his PhD (with honors, advisors Dr. González and Dr. García) from the University of Oviedo in 2015 – both in Electronics Engineering. After completing his M.S., he gained industry experience working for technological companies in Basingstoke, UK, and Berkeley, CA, USA. As a PhD student, he was awarded with a predoctoral research fellowship for a 6-month stay at the Electrochemical Power Systems Laboratory (advisors Dr. Liaw and Dr. Dubarry), at the University of Hawaii, USA, where he was introduced to the use of new techniques for the analysis of the degradation of Li-ion cells. After completing his PhD, he returned to the University of Hawaii as a post-doctoral fellow (advisors Dr. Dubarry and Dr. Devie) to work on advanced diagnosis and prognosis techniques on lithium-ion batteries. He re-joined the University of Oviedo in 2017 as an Assistant Professor, where he teaches a variety of courses including Instrumentation Engineering, Digital Integrated Circuits and Electronics Technology.

About the author

Matthieu Dubarry (PhD, Electrochemistry & Solid State Science, University of Nantes), has over 15 years of experience in renewable energy, with an emphasis in the area of lithium ion batteries. Following his PhD on the synthesis and characterization of materials for lithium batteries, Dr. Dubarry joined the Hawaii Natural Energy Institute at the University of Hawaii at Mānoa as a post-doctoral fellow in 2005 to work on the analysis of the usage of a fleet of electric vehicles.

He was later appointed a faculty position in 2010 with a focus on battery testing, modeling and simulation. While working for HNEI, Dr. Dubarry pioneered the use of new techniques for the analysis of the degradation of Li-ion cells and developed numerous software tools facilitating the prognosis of Li-ion battery degradation both at the single cell and the battery pack level. Current projects include the evaluation of grid scale Li-ion battery energy storage systems; the evaluation of the impact of vehicle-to-grid strategies on electric vehicle battery pack degradation; and the testing of emerging battery technologies for grid-connected and transportation applications.

About the author

Dr. Arnaud Devie received his M.Sc. degree in Electrical Engineering in 2009 from INSA Lyon, France. He then studied lithium-ion batteries usage in EV and HEV applications while pursuing his Ph.D. at the University of Lyon in collaboration with the French Institute of Science and Technology for Transport, Development and Networks (IFSTTAR). Dr. Devie later joined the Hawaii Natural Energy Institute (HNEI) at the University of Hawaii at Mānoa in 2013 to work on lithium-ion battery degradation diagnosis with Dr. Dubarry and Dr. Liaw.

His research interests include cell design, battery aging, degradation diagnosis, abuse, cell-to-cell variations, modeling and simulation of battery systems, and battery management systems for SOC and SOH estimation. Dr. Devie joined Maxim Integrated as a Senior Battery Scientist in 2017.

About the author

Boryann Liaw, Ph.D.
Department Manager, Energy Storage and Advanced Vehicles
Idaho National Laboratory

Dr. Boryann (Bor Yann) Liaw is manager of the Energy Storage and Advanced Vehicles Department at Idaho National Laboratory. The department operates state-of-the-art Battery Test Center, Non-destructive Battery Evaluation Laboratory, and Electric Vehicle Infrastructure Laboratory, to conduct reliability, safety, and failure analyses of energy storage systems, advanced vehicles, and charging infrastructure and equipment. Before joining INL, Dr. Liaw was a specialist and tenured faculty member at the Hawaii Natural Energy Institute of the University of Hawaii at Manoa. At HNEI, he focused on advanced power source systems for vehicle and energy storage applications. He received his bachelor’s in chemistry from the National Tsinghua University in Taiwan, his master’s in chemistry from the University of Georgia, and his doctorate in materials science and engineering from Stanford University. He conducted his post-doctoral fellowship research at the Max-Plank Institute of Solid State Research in Stuttgart, Germany.

For the past three decades, Dr. Liaw has been involved in R&D projects related to electric and hybrid vehicle evaluation and advanced battery diagnostics and prognostics. His major research activities comprise laboratory and real-life battery and vehicle testing, data collection and analysis, battery modeling and simulation, battery performance and life prediction, battery rapid charging technology development, and battery diagnoses and prognoses. He also expanded his endeavors to bio-fuel cells, including sugar-air alkaline battery development, and transforming ambient energy resources into useful power sources for portable or stationary applications. Dr. Liaw has co-authored more than 150 technical papers, seven book chapters, and eight patents and patent applications. He is a Fellow of the Electrochemical Society. For ECS, he has served as chair of the Battery Division, associate editor, and member of the Editorial Board and Meetings Subcommittee.

About the author

Víctor Manuel García Fernández received the M.Sc. Degree and the Ph.D. in Chemistry from the University of Oviedo. Currently he is an Associate Professor in the area of Physical Chemistry, where he teaches Applied Electrochemistry, focusing on quantitative description of thermodynamics (theory of intercalation), kinetics (charge transfer mechanisms on interfaces) and bulk transport phenomena of batteries and electrochemical corrosion cells.

His research is currently focused on the electrical, chemical and thermal characterization and modeling (physical and semi physical) of high power lithium ion cells with nanophosphate chemistry, where he is involved in several research projects on said technology. He is also investigating the combination of electrochemical impedance spectroscopy, incremental capacity analysis and first principles modeling to obtain physically meaningful equivalent circuit models suitable for characterizing degradation in electrochemical cells subject to dynamic discharge protocols.

About the author

Juan Carlos Viera Pérez received his Ph.D. degree from the University of Oviedo, Spain, in 2003, where he is an Associate Professor in the Electrical Engineering Department. He is the coordinator of the R&D activities of the Battery Research Laboratory at the Campus of Gijon of the University of Oviedo. Dr. Viera has over 20 years’ battery researching experience, and his main interest include energy storage systems, new advanced battery technologies, and battery management systems, focusing on the design of battery test benches, electrical and chemical characterization under standard/stressful conditions, thermal behaviour, and efficient fast-charging methods.

Dr. Viera leads and collaborates with several projects related to advanced battery technologies and their applications, especially in the field of electric vehicles and battery energy storage systems. He is a senior member of the Institute of Electrical and Electronics Engineers (IEEE).

About the author

Manuela González, Ph.D.
Head of Battery Research Laboratory
Department of Electrical Engineering
University of Oviedo, Spain
Email: [email protected]

Dr. Manuela González received the M.Sc. and the Ph.D. degrees in Electrical Engineering from the University of Oviedo, Spain, in 1992 and 1998, respectively. She is the founder and Head of the “Batteries and new energy storage systems” research group in the Electrical Engineering Department of University of Oviedo, a multidisciplinary team (PhDs in Electrical and Electronics Engineering, Computer Science and Chemistry) that focuses its research on the electrical and chemical characterization of batteries, and the design of efficient fast-charging and management methods. With more than 20 years of experience in the field of battery testing, she is the manager of the Battery Research Laboratory at the Campus of Gijon (University of Oviedo).

Her research focuses on new Li-ion technologies for transportation and energy storage systems applications, including the development of advanced state-of-health estimation methods. Dr. Manuela González has collaborated in more than 25 R&D battery related projects, combining the research with the transference of results to companies.


Anseán, M. Dubarry, A. Devie, B.Y. Liaw, V.M. García, J.C. Viera, M. González. Operando lithium plating quantification and early detection of a commercial LiFePO4 cell cycled under dynamic driving schedule. Journal of Power Sources, volume 356 (2017), pages 36-46.


Go To Journal of Power Sources

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