Lithium Plating Mechanism, Detection, and Mitigation in Lithium-Ion Batteries

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Abstract

The success of electric vehicles depends largely on energy storage systems. Lithium-ion batteries have many important properties to meet a wide range of requirements, especially for the development of electric mobility. However, there are still many issues facing lithium-ion batteries. One of the issues is the deposition of metallic lithium on the anode graphite surface under fast charging or low-temperature conditions. Lithium plating reduces the battery life drastically and limits the fast-charging capability. In severe cases, lithium plating forms lithium dendrite, which penetrates the separator and causes internal short. Significant research efforts have been made over the last two decades to understand the lithium plating mechanisms. However, the lithium plating mechanisms have not yet been fully elucidated. Meanwhile, another challenge in the development of fast charging technologies is to identify degradation mechanisms in real-time. This includes real-time detection of lithium plating while the battery is being charged. Accurate detection and prediction of lithium plating are critical for fast charging technologies. Many approaches have been proposed to mitigate lithium plating, such as adopting advanced material components and introducing hybrid and optimized charging protocols. Nevertheless, most detection techniques and mitigation strategies are only used for fundamental research with limited possibilities in large-scale applications. To date, there is still a lack of a comprehensive review of lithium plating, reflecting state of the art and elucidating potential future research directions. Therefore, in this article, we provide a snapshot of recent advances in lithium plating research in terms of mechanism, detection, and mitigation to fill this gap and incentivize more innovative thoughts and techniques. In the present study, the mechanisms of lithium plating and approaches used to characterize and detect it in different applications are carefully reviewed. This review also provides a summary of recent advances in model-based approaches to predict lithium plating. Based on the gathered information, the advantages and drawbacks of each model are compared. The mitigation strategies for suppressing lithium plating at different levels are studied. Finally, we highlighted some of the remaining technical challenges and potential solutions for future advancement.

Introduction

The transportation sector is one of the largest contributors to global greenhouse gas (GHG) emissions [1], [2], [3]. The negative effect of GHG on human life and the environment provides a strong driving force for reducing GHG emissions [4]. Transportation electrification is a promising solution to alleviate the growing concern about GHG emissions. More and more electric vehicles (EVs), hybrid electric vehicles (HEVs), and plug-in hybrid electric vehicles (PHEVs) have been developed and deployed as alternatives to traditional internal combustion engine (ICE) vehicles [4], [5], [6]. The success of transportation electrification depends largely on energy storage systems. As one of the most promising energy storage systems, lithium-ion batteries (LiBs) have many important properties to meet the wide range of requirements of electric mobility [7,8]. The challenging requirements for further development of the LiB system are longer life, fast charging, low-temperature charging, self-recovery capability, and safety performance. In fact, according to the literature, these requirements are related to the aging mechanisms of lithium plating and anode kinetics. Precise diagnosis, prognosis and understanding of the mechanisms and effects of lithium plating on the performance of cells and battery packs are critical to the optimal design and safe operation of LiB systems. However, due to the complex, nonlinear, and path-dependent nature of battery degradation [9,10], the aging mechanisms are not fully understood. As a result, as shown in Fig. 1, lithium plating has been the subject of several levels of research, ranging from understanding the mechanism of lithium plating to demonstrate why, where, when, and under what conditions this phenomenon occurs, to determining the most effective method to detect, predict, and prevent it. Therefore, the purpose of this article is to review the existing work in the literature and identify some of the fundamental knowledge gaps at each of these levels.

A typical lithium-ion battery cell, as shown in Fig. 2 (A), comprises a composite negative electrode, separator, electrolyte, composite positive electrode, and current collectors [11,12]. The composite negative electrode has a layered and planner crystal structure that is placed on the copper foil, which functions as a current collector. There are three types of carbonaceous materials: graphite, graphitizable carbon, and non-graphitizable carbon (hard carbon) [11,13]. Graphite is frequently used as a negative electrode because of its excellent performance, low cost, and non-toxicity [14]. The composite positive electrode (cathode) is a metal-oxide with a tunneled or layered structure that is coated with aluminum foil [15]. Aluminum acts as a current collector. The electrolyte plays a critical role in the lithium-ion diffusion process. The electrolyte allows lithium ions to move between electrodes [13,16]. The separator is a piece of thin microporous polymer film (10 to 30 μm) soaked in the electrolyte and sandwiched between the anode and cathode electrodes to prevent shorting of the two electrodes [11].

During the normal charging process, electrons are extracted from the cathode and moved to the anode through the external circuit by the charger. Meanwhile, Li+ ions are de-intercalated from the cathode and moved to the anode through electrolyte [14]. During discharge, the entire procedure is reversed. The lithium-ion intercalation process (during charging) has three major steps [17]: (i) the Li+ ions diffuse out of the cathode, (ii) the diffusion of solvated Li+ions in the electrolyte, (iii) de-solvation Li+ ions pass through the SEI and intercalate into the interlayer of graphite [18], [19], [20]. Step (iii), generally known as the charge-transfer process, is broken into three subprocesses [21,22]: 1) de-solvation of solvated Li+ ions (strip off their solvation shell), 2) naked Li+ passing through the SEI, and 3) solid-state lithium diffusion into graphite (Li+ reaching the anode and receiving an electron, which could occur at the anode-SEI interface or the anode-electronic conductor-SEI interface [18]) (Fig. 2 (C)). These steps would be favored in an ideal battery working condition. Nonetheless, in real-world applications, LiBs are subjected to a variety of severe working conditions, which have a substantial impact on battery performance and longevity.

Battery degradation is a complicated issue involving numerous physical and chemical processes. Degradation is dependent on a number of complex mechanisms caused by a variety of factors (e.g., intrinsic and extrinsic) [23,24]. Intrinsic factors are classified into two categories: material properties and manufacturing procedures [25]. Extrinsic factors derive from the LiB operating conditions, such as charging at a high C-rate, high state of charge (SOC), or low temperature [23,24]. As shown in Fig. 3, the aging mechanisms affect not only the anode and cathode electrodes, but also other LiB components such as electrolyte, separator, binder, and current collector [25], [26], [27]. The most detrimental aging mechanisms impacting graphite anode electrodes are solid electrolyte interphase (SEI) film growth, binder decomposition, and lithium plating [28], [29], [30]. According to the literature, aging mechanisms can be divided into three main degradation modes (DMs): loss of lithium inventory (LLI), loss of active materials (LAM) [31], and loss of electrolyte [25,32]. In LLI, lithium ions are consumed by side reactions, such as SEI film formation and irreversible plating [33]. Since these lithium ions are no longer cyclable for the intercalation process, the cell capacity is reduced (capacity fade) [34,35]. LAM, on the other hand, is usually related with structural changes and material loss [23]. The active mass on the anode is reduced due to graphite exfoliation, electrode particle cracking, or dead lithium blocking the active site pathway. Furthermore, the active mass of the cathode is reduced due to transition metal dissolution, structural disordering, and electrode particle cracking [27,34,36,37]. The other significant cause of degradation is electrolyte loss; the deposited lithium on the anode interface reacts with the electrolyte, consuming the electrolyte [16,32]. The significant reduction in electrolyte content may result in capacity and power fading at the end of the battery's life.

Among the several aging mechanisms in LiBs, one of the most detrimental is the deposition of metallic lithium or lithium plating on the graphite anode surface. This is due to the fact that lithium plating may not only promote further degradation, but it may also have a negative impact on the safety of LiBs [38]. During fast charging, lithium-ions can be deposited on the surface of the graphite anode rather than being intercalated into the interstitial space between the graphite anode's atomic layers [39]. In general, the deposited lithium can be reversible or irreversible. The irreversible portion can react with the electrolyte to form a secondary SEI layer, or it can form a high-impedance “dead” lithium film that is electrically isolated from the graphite anode and remains irreversible, increasing internal resistance and decreasing energy density [29,40]. The irreversible portion causes capacity fade to be accelerated. In severe cases, the accumulated lithium might also form a dendrite. Dendrites can develop and pierce the separator [41]. The reversible portion describes the deposited lithium with an electrical contact on the anode interface, which can undergo charge transfer reaction into the electrolyte and subsequently re-intercalate into the anode, this process is known as lithium stripping. The stripping process occurs throughout the rest or discharge process following lithium plating [42,43]. One of the major limiting factors for fast charging is lithium plating. As a result, one of the major difficulties of fast charging technologies is to prevent or mitigate lithium plating during the charging process.

Several studies have been conducted, including investigations into lithium plating mechanisms at various charging conditions, the development of effective detection techniques, and the development of strategies for mitigating lithium plating. Fig. 4 (A) and (B) outline the various charging currents (C-rates), testing temperatures, and commercial cell types used in the literature to study lithium plating. The C-rate is the current value that discharges a battery within 1 h from a fully charged state to a fully discharged state [44]. It is generally known in battery testing as a current value equal to a cell's rated capacity (Ah). The test temperature varies from study to study and might range from -60 °C to 80 °C. According to our findings, the majority of the studies tested the cells at room temperature (25 °C) at 1 C. Some studies at higher C-rates and lower temperatures have also been conducted.

Several studies investigated lithium plating at lower charging rates (0.3 and 0.5 C-rate) and temperature ranges from (-20 °C to 40 °C). However, further research on lithium plating at lower temperatures and greater C-rates is still necessary. Various types of commercial cells were employed in the literature to study lithium plating, ranging from 18650 and 26650 types (1.5 Ah to 3.4 Ah) to large-scale pouch types (9.5 Ah to 16 Ah). In the literature, various battery cells are used for investigating lithium plating. Most of them use graphite as the anode and use different cathode materials, such as lithium nickel cobalt manganese oxide (NMC 111), lithium iron phosphate (LFP), and lithium cobalt oxide (LCO).

The overarching goal of this paper is to provide a timely, comprehensive review of the latest progress of lithium plating in the existing literature, to gain a better understanding of lithium plating. Since graphite has been widely used as the anode in commercial LiBs, this work is focused on studying lithium plating in batteries that use graphite as the anode. The most recent studies on lithium plating on graphite anode are thoroughly reviewed. The mechanisms of lithium plating and the chemical reactions that contribute to lithium plating under various conditions are discussed. Recent approaches for detecting lithium plating are thoroughly explored and compared. Each detection method's applicability is also investigated. The existing electrochemical models used to simulate cell behavior in order to predict lithium plating are studied and explained. Additionally, optimal and common charging protocols are introduced. In conclusion, based on the literature, research gaps are identified, and suggestions for future research directions are provided.

Section snippets

Lithium Plating Reactions

Lithium plating is a parasitic process that goes along with the lithium intercalation process. Equation (1) shows the complete insertion of Li+ ions into the graphite anode electrode. Intercalation is a diffusion-limited process, meaning that a certain amount of Li+ ions can be embedded into the interlayer of graphite per unit time at a given temperature [37]. The potential range for Li+ ions insertion inside the graphite is 65-200 mV vs. Li+/Li [29]. Equation (2) shows partial or full

Main Factors Affecting Lithium Plating

Many research efforts have been undertaken to understand how, where and why lithium plating occurs during both normal and fast charging conditions. However, the mechanisms of lithium plating have not been fully elucidated due to its complex nature [53]. According to numerous previous researches, lithium plating occurs as a result of three major factors, which include but are not limited to: (i) hazardous operating conditions, (ii) cell defects, and (iii) aging of the cell (Table 1) [54].

Lithium Plating Detection Approaches

Detecting lithium plating in its early stages is often challenging. To understand the formation and growth of lithium plating, extensive efforts have been made in the past to characterize and observe the anode lithium plating morphology [83]. Many approaches (in-situ, ex-situ, non-destructive, and recently in-operando methods) have been proposed by researchers to investigate lithium plating mechanisms in LiBs. These detection methods are classified into three main categories: (i) physical

Model-Based Investigation of Lithium Plating

In order to optimize the battery design and develop more practical charging protocols, model-based approaches are a good option [7,35,202]. There are several different approaches to model LiBs: electrochemical models, equivalent-circuit battery models (ECM), thermal models, electrical models, mechanical models, and molecular models [203]. Modeling provides us with the exact time of lithium plating and the location of the deposited lithium on the electrode surface. Newman [204] and co-workers

Effect of Material Components and Charging Protocols on Lithium Plating

As shown in Fig. 10, developing high-performance fast-charging LiB without lithium plating requires a multidisciplinary approach. The previous sections have provided a comprehensive overview of the mechanisms, detection, and prediction of lithium plating. Extensive efforts have been made at multiple levels, including material component modification (electrode and electrolyte interfaces), cell and pack design optimization, charging protocol optimization, and the development of a battery

Challenges and Future Trends

Lithium plating has been widely investigated in the last decade. However, some problems remain, such as accurate and reliable detection methods, mechanisms, prediction, and prevention. In this section, challenges and prospects are introduced in the aspects of mechanisms, detection methods, modeling, material components, and optimized charging protocols.

Conclusions

In this paper, the current literature on lithium plating was reviewed. Degradation of LiBs during operation is one of the most complicated and critical issues that involve the variety of electrochemical side reactions in all the LiB components. Lithium plating is one of the most important degradation mechanisms of the anode electrode. The main impact of lithium plating is severe capacity fade. It occurs under three main working conditions: low-temperature charging, high C-rate charging, and

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

XL acknowledges support by the Natural Sciences and Engineering Research Council of Canada (NSERC) through the NSERC Early Career Researcher Supplement & Discovery Grant Program (RGPIN-2018-05471) and Ontario Tech University Startup Fund. XH acknowledges support by the National Natural Science Foundation of China (Grant no. 51875054 and Grant no. U1864212). JL acknowledges support by Wuxi Weifu High-Technology Group Co., Ltd.

Xianke Lin received the BS degree from Zhejiang University, Hangzhou, China, in 2009, and the Ph.D. degree in mechanical engineering from the University of Michigan, Ann Arbor, MI, USA, in 2014. He has extensive industrial experience with Fiat Chrysler Automobiles, Auburn Hills, MI, USA, Mercedes-Benz Research & Development North America, Detroit, MI, USA, and General Motors of Canada, Oshawa, ON, Canada. He is currently an Assistant Professor with the Department of Automotive and Mechatronics

References (275)

  • M Ouyang et al.

    Low temperature aging mechanism identification and lithium deposition in a large format lithium iron phosphate battery for different charge profiles

    J Power Sources

    (2015)
  • J Vetter et al.

    Ageing mechanisms in lithium-ion batteries

    J Power Sources

    (2005)
  • N Legrand et al.

    Physical characterization of the charging process of a Li-ion battery and prediction of Li plating by electrochemical modelling

    J Power Sources

    (2014)
  • C Pastor-Fernández et al.

    A Study of Cell-to-Cell Interactions and Degradation in Parallel Strings: Implications for the Battery Management System

    J Power Sources

    (2016)
  • M Dubarry et al.

    Synthesize battery degradation modes via a diagnostic and prognostic model

    J Power Sources

    (2012)
  • CR Birkl et al.

    Degradation diagnostics for lithium ion cells

    J Power Sources

    (2017)
  • F Grimsmann et al.

    Impact of different aging mechanisms on the thickness change and the quick-charge capability of lithium-ion cells

    J Energy Storage

    (2017)
  • S Ahmed et al.

    Enabling fast charging – A battery technology gap assessment

    J Power Sources

    (2017)
  • R. Chandrasekaran

    Quantification of bottlenecks to fast charging of lithium-ion-insertion cells for electric vehicles

    J Power Sources

    (2014)
  • S Hein et al.

    Influence of local lithium metal deposition in 3D microstructures on local and global behavior of Lithium-ion batteries

    Electrochim Acta

    (2016)
  • SJ Harris et al.

    Direct in situ measurements of Li transport in Li-ion battery negative electrodes

    Chem Phys Lett

    (2010)
  • A Barai et al.

    A comparison of methodologies for the non-invasive characterisation of commercial Li-ion cells

    Prog Energy Combust Sci

    (2019)
  • M Ecker et al.

    Influence of operational condition on lithium plating for commercial lithium-ion batteries – Electrochemical experiments and post-mortem-analysis

    Appl Energy

    (2017)
  • X Zhao et al.

    Electrochemical-thermal modeling of lithium plating/stripping of Li(Ni0.6Mn0.2Co0.2)O2/Carbon lithium-ion batteries at subzero ambient temperatures

    J Power Sources

    (2019)
  • XG Yang et al.

    A look into the voltage plateau signal for detection and quantification of lithium plating in lithium-ion cells

    J Power Sources

    (2018)
  • E Sahraei et al.

    Characterizing and modeling mechanical properties and onset of short circuit for three types of lithium-ion pouch cells

    J Power Sources

    (2014)
  • CJ Orendorff et al.

    Experimental triggers for internal short circuits in lithium-ion cells

    J Power Sources

    (2011)
  • D Anseán et al.

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

    J Power Sources

    (2017)
  • T Guan et al.

    The degradation of LiCoO2/graphite batteries at different rates

    Electrochim Acta

    (2018)
  • L Gireaud et al.

    Lithium metal stripping/plating mechanisms studies: A metallurgical approach

    Electrochem Commun

    (2006)
  • M Petzl et al.

    Lithium plating in a commercial lithium-ion battery - A low-temperature aging study

    J Power Sources

    (2015)
  • J Jaguemont et al.

    A comprehensive review of lithium-ion batteries used in hybrid and electric vehicles at cold temperatures

    Appl Energy

    (2016)
  • S Ma et al.

    Temperature effect and thermal impact in lithium-ion batteries: A review

    Prog Nat Sci Mater Int

    (2018)
  • M Börner et al.

    Degradation effects on the surface of commercial LiNi0.5Co0.2Mn0.3O2 electrodes

    J Power Sources

    (2016)
  • XG Yang et al.

    Asymmetric Temperature Modulation for Extreme Fast Charging of Lithium-Ion Batteries

    Joule

    (2019)
  • P Keil et al.

    Charging protocols for lithium-ion batteries and their impact on cycle life-An experimental study with different 18650 high-power cells

    J Energy Storage

    (2016)
  • S Liu et al.

    Long cycle life lithium ion battery with lithium nickel cobalt manganese oxide (NCM) cathode

    J Power Sources

    (2014)
  • SF Schuster et al.

    Nonlinear aging characteristics of lithium-ion cells under different operational conditions

    J Energy Storage

    (2015)
  • T Waldmann et al.

    Temperature dependent ageing mechanisms in Lithium-ion batteries - A Post-Mortem study

    J Power Sources

    (2014)
  • A Friesen et al.

    Impact of cycling at low temperatures on the safety behavior of 18650-type lithium ion cells: Combined study of mechanical and thermal abuse testing accompanied by post-mortem analysis

    J Power Sources

    (2016)
  • T Rauhala et al.

    Low-temperature aging mechanisms of commercial graphite/LiFePO4 cells cycled with a simulated electric vehicle load profile—A post-mortem study

    J Energy Storage

    (2018)
  • M Kassem et al.

    Postmortem analysis of calendar-aged graphite/LiFePO4 cells

    J Power Sources

    (2013)
  • M Lang et al.

    Post mortem analysis of fatigue mechanisms in LiNi0.8Co0.15Al0.05O2 – LiNi0.5Co0.2Mn0.3O2 – LiMn2O4/graphite lithium ion batteries

    J Power Sources

    (2016)
  • M Storch et al.

    Post-mortem analysis of calendar aged large-format lithium-ion cells: Investigation of the solid electrolyte interphase

    J Power Sources

    (2019)
  • J Steiger et al.

    Mechanisms of dendritic growth investigated by in situ light microscopy during electrodeposition and dissolution of lithium

    J Power Sources

    (2014)
  • J Steiger et al.

    Microscopic observations of the formation, growth and shrinkage of lithium moss during electrodeposition and dissolution

    Electrochim Acta

    (2014)
  • C Uhlmann et al.

    In situ detection of lithium metal plating on graphite in experimental cells

    J Power Sources

    (2015)
  • British Petroleum

    BP Energy Outlook 2019 edition The Energy Outlook explores the forces shaping the global energy transition out to 2040 and the key uncertainties surrounding that

    BP Energy Outlook 2019

    (2019)
  • K. Popham

    Transportation electrification

    Smart Cities Appl Technol Stand Driv Factors

    (2017)
  • R Zhang et al.

    The role of transport electrification in global climate change mitigation scenarios

    Environ Res Lett

    (2020)
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    Xianke Lin received the BS degree from Zhejiang University, Hangzhou, China, in 2009, and the Ph.D. degree in mechanical engineering from the University of Michigan, Ann Arbor, MI, USA, in 2014. He has extensive industrial experience with Fiat Chrysler Automobiles, Auburn Hills, MI, USA, Mercedes-Benz Research & Development North America, Detroit, MI, USA, and General Motors of Canada, Oshawa, ON, Canada. He is currently an Assistant Professor with the Department of Automotive and Mechatronics Engineering, Ontario Tech University, Oshawa, Canada. His research activities have concentrated on hybrid powertrain design and control strategy optimization, multiscale/multiphysics modeling, and optimization of energy storage systems.

    Kavian Khosravinia received the BS degree in automotive engineering from Azad University of Khomeinishahr, Iran in 2012. And Master of Science in Automotive Engineering in University Putra Malaysia in 2018. He is currently pursuing the Ph.D. degree in automotive engineering at Ontario Tech University. His research interests include battery degradation modeling and fast charging technologies.

    Xiaosong Hu received the Ph.D. degree in automotive engineering from Beijing Institute of Technology, China, in 2012. He did scientific research and completed the Ph.D. dissertation in Automotive Research Center at the University of Michigan, Ann Arbor, USA, between 2010 and 2012. He is currently a Professor at the State Key Laboratory of Mechanical Transmissions and at the Department of Automotive Engineering, Chongqing University, Chongqing, China. He was a postdoctoral researcher at the Department of Civil and Environmental Engineering, University of California, Berkeley, USA, between 2014 and 2015, as well as at the Swedish Hybrid Vehicle Center and the Department of Signals and Systems at Chalmers University of Technology, Gothenburg, Sweden, between 2012 and 2014. He was also a visiting postdoctoral researcher in the Institute for Dynamic systems and Control at Swiss Federal Institute of Technology, Zurich, Switzerland, in 2014. His research interests include battery management technologies and modeling and controls of electrified vehicles. He has been a recipient of several prestigious awards/honors, including SAE Ralph Teetor Educational Award in 2019, Emerging Sustainability Leaders Award in 2016, EU Marie Currie Fellowship in 2015, ASME DSCD Energy Systems Best Paper Award in 2015, and Beijing Best Ph.D. Dissertation Award in 2013.

    Ju Li received the BS degree in Physics from the University of Science and Technology of China in 1994, and the Ph.D. degree in nuclear engineering from the Massachusetts Institute of Technology, USA, in 2000. He is currently the Battelle Energy Alliance Professor of Nuclear Science and Engineering at Massachusetts Institute of Technology. He has received TMS Robert Lansing Hardy Award and MRS Outstanding Young Investigator Award. A highly cited expert in his field, he is also a Fellow of the Materials Research Society and American Physical Society.

    Wei Lu received his Ph.D. from the Mechanical and Aerospace Engineering Department, Princeton University, and joined the faculty of Mechanical Engineering Department, the University of Michigan in 2001. He received his BS from Tsinghua University, China. His research interests include energy storage and electrochemistry; simulation of nano/microstructure evolution; mechanics in nano/micro systems; advanced manufacturing; mechanical properties and performance of advanced materials and relation to microstructures. Prof. Lu was the recipient of many prestigious awards including the CAREER award by the US National Science Foundation, the Robert J. McGrattan Award by the American Society of Mechanical Engineers, Elected Fellow of the American Society of Mechanical Engineers, Robert M. Caddell Memorial Research Achievement Award, Faculty Recognition Award, Department Achievement Award, Distinguished Professor Award, Novelis and College of Engineering, Ted Kennedy Family Faculty Team Excellence Award, CoE George J. Huebner, Jr. Research Excellence Award, and the Gustus L Larson Memorial Award by the American Society of Mechanical Engineers. He was invited to the National Academies Keck Futures Initiative Conference multiple times.

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