Learning from Overpotentials in Lithium Ion Batteries: A Case Study on the LiNi1/3Co1/3Mn1/3O2(NCM) Cathode

Kasnatscheew, Johannes; Rodehorst, Uta; Streipert, Benjamin; Wiemers‐Meyer, Simon; Jakelski, Rene; Wagner, Ralf; Laskovic, Isidora Cekic; Winter, Martin

doi:10.1149/2.0461614jes

Cited by 123 publications

(135 citation statements)

References 74 publications

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“…41-44 and 45; original research on the material can be found in Ref. [50][51][52][53][54][55][56][57][58][59][60]. In this work, we apply our thermodynamic modeling to Ni 0.6 Mn 0.2 Co 0.2 .…”

Section: Discussion Of Resultsmentioning

confidence: 99%

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Thermodynamic Model for Substitutional Materials: Application to Lithiated Graphite, Spinel Manganese Oxide, Iron Phosphate, and Layered Nickel-Manganese-Cobalt Oxide

Baker

Koch²,

Xiao

et al. 2017

J. Electrochem. Soc.

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We derive and implement a method to describe the thermodynamics of electrode materials based on a substitutional lattice model. To assess the utility and generality of the method, we compare model results with experimental data for a variety of electrode materials: lithiated graphite and layered nickel-manganese-cobalt oxide (Chevrolet Bolt Electric Vehicle negative and positive electrode materials, respectively), manganese oxide (in the positive electrodes of the Gen 1 and Gen 2 Chevrolet Volt Extended Range Electric Vehicle and the positive electrode of many high-power-density batteries), and iron phosphate (Gen 1 Chevrolet Spark Electric Vehicle positive electrode material and of immediate interest for 12 and 48 V applications). An early version of the model has been applied to lithiated silicon (Li-Si). As was found in the Li-Si study, the model enables one to quantitatively represent experimental data from these different electrode materials with a small number of parameters, and, in this sense, the approach is both general and efficient. An open question is the utility of controlled-potential vs. controlled-current experiments for the elucidation of the system thermodynamics. We provide commentary on this question, and we highlight other open questions throughout this work. Central to the modeling of electrochemical systems, particularly batteries relying on solid-state diffusion within the active materials, is an accurate description of the system thermodynamics.1-4 We describe and implement a thermodynamic model for substitutional electrode materials. At the heart of the model is a simple expression for the open-circuit potential U in terms of the fraction of filled sites x within a host material. To assess the value of the model, we apply it to four electrode materials of commercial interest today: lithiated graphite, spinel manganese oxide, iron phosphate, and nickel-manganese-cobalt oxide. The model is an expanded version of that described in Ref. 12. A slight alteration is needed to describe the nickel-manganese-cobalt oxide so that inaccessible lithium can be considered (giving rise to x 0 in Table I), and we also describe how reactions between sites within the electrode material can be addressed.This document is organized as follows. First, we provide an overview of the materials and instrumentation for the experimental characterization of the electrode materials. An introduction of the thermodynamic model is then presented, followed by a detailed description of the model. A discussion of results is then presented, followed by a brief Appendix devoted to the convergence properties of the series summation employed in the U(x) model. • C under about 0.01 Torr vacuum. Other materials were dried at 100 Experimental• C under vacuum of about 0.01 Torr. Cell assembly and cycling were performed under an inert argon atmosphere with O 2 and H 2 O concentrations < 1 ppm. Cycling was performed with a Princeton Applied Research PMC 2000 potentiostat/galvanostat. For the voltammetry work on the Ni 0.6 Mn 0.2 Co ...

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Section: Discussion Of Resultsmentioning

confidence: 99%

“…Recent investigations of this aspect of NMC can be found in References 58 and 59; see, in particular, Figure 5 of Ref. 58 and the associated discussion with respect to the inability to remove all Li from NMC at potentials yielding stable performance.…”

Section: Discussion Of Resultsmentioning

confidence: 99%

Thermodynamic Model for Substitutional Materials: Application to Lithiated Graphite, Spinel Manganese Oxide, Iron Phosphate, and Layered Nickel-Manganese-Cobalt Oxide

Baker

Koch²,

Xiao

et al. 2017

J. Electrochem. Soc.

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“…Fort he sameL iMO 2 -type electrode material, the amount of extracted Li + is proportional to the applied chargec ut-off potential;t hus,i tc an be concluded that the structural stability of LiMO 2 -type electrodesi sp rimarily determined by the amounto fe xtracted Li + ions. [16,22,23] In the literature,t he structural stability and stability versus transition-metal dissolution of various,t hat is,not the same cathode materials,positive electrode material has been compared and discussed as af unctiono ft he applied charge cut-off potential. [19,24,25] However, ac omparison between different LiMO 2 -type electrode materials with regard to their structural stability is only reasonable as af unction of the amount of extracted Li + ions.…”

Section: Introductionmentioning

confidence: 99%

Learning from Electrochemical Data: Simple Evaluation and Classification of LiMO₂‐type‐based Positive Electrodes for Li‐Ion Batteries

et al. 2017

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The required boost in the specific energy of lithium‐ion battery (LIB) cells can only be achieved by increasing the cell voltage and/or the specific capacities of the electrodes. In the latter regard, the positive electrode constitutes the specific energy bottleneck. Lithium transition‐metal oxides (LiMO2) such as LiNixMnzCo1−x−zO2 (NMC) are regarded as the most suitable positive electrode materials for next‐generation high‐specific‐energy LIBs. In this work, the electrochemically induced structural stability limits as well as the associated reversible specific energies and specific energy efficiencies were assessed by means of constant current charge/discharge experiments for the most popular and promising LiMO2 compositions. The electrochemically induced structural stability of the positive host material was not determined by the applied charge cut‐off potential, but rather by the amount of extracted Li+ ions. In this regard, the electrochemically induced structural stability order of selected LiMO2 compositions was modified by assessing the structural stability as a function of the Li+‐ion extraction ratio. With respect to application, relevant requirements (e.g., specific energy, specific energy efficiency, temperature‐dependent structural stability, kinetics) revealed that NMC532 and NMC622 showed the best compromise among the various LiMO2 compositions, revealing significant insight into the structure–property relationship.

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“…NMC333 has been the focus of several articles related to synthesis, kinetic and transport properties estimation and performance rate study. 13,21 For NCM523, a few characterization studies have come out in the past decade. Yang et al 22 used Galvanostatic Intermittent * Electrochemical Society Student Member.…”

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confidence: 99%

Galvanostatic Intermittent Titration and Performance Based Analysis of LiNi_0.5Co_0.2Mn_0.3O₂Cathode

Verma

Smith

Santhanagopalan

et al. 2017

J. Electrochem. Soc.

122

127

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Galvanostatic intermittent titration technique (GITT) -a popular method for characterizing kinetic and transport properties of battery electrodes -is predicated on the proper evaluation of electrode active area. LiNi 0.5044 Co 0.1986 Mn 0.2970 O 2 (NCM523) material exhibits a complex morphology in which sub-micron primary particles aggregate to form secondary particle agglomerates. This work proposes a new active area formulation for primary/secondary particle agglomerate materials to better mimic the morphology of NCM532 electrodes. This formulation is then coupled with macro-homogeneous models to simulate GITT and half-cell performance of NCM523 electrodes. Subsequently, the model results are compared against the experimental results to refine the area formulation. A single parameter, the surface roughness factor, is proposed to mimic the change in interfacial area, diffusivity and exchange current density simultaneously and detailed modeling results are presented to provide valuable insights into the efficacy of the formulation. Lithium ion batteries (LIBs) are ubiquitous in energy storage applications. LIBs are versatile and have completely penetrated the consumer electronics market involving low power applications, e.g. mobile phones and laptops.1 In recent years, the use of LIBs in high power applications like electric vehicles is showing great promise. Consequently, vigorous efforts are being directed toward improving its capacity and rate capabilities. LIB energy and power density is directly related to the constituent anode/cathode chemistries. The couples are chosen such that potential difference between the electrodes and Li + ions storage capacity are maximized. Additionally, fast intercalation and diffusion in the solid phase are required for high energy efficiency at high power demands. For anode, graphite has proved to be a valuable material with maximum theoretical capacity estimated at 372 mAh/g graphite combined with open circuit potential close to 0.0 V vs Li for wide range of state of charge. Graphite as an anode material shows robust cycling performance, decent rate capabilities and satisfactory thermal stability.3,4 Current cathodes generally exhibit lower theoretical capacity compared to anodes. Thus, a significant share of research efforts have been concentrated on finding and characterizing novel LIB cathode materials.Several It is apparent that GITT and EIS have emerged as robust electrochemical techniques for battery material characterization. However, extraction of accurate kinetic and transport quantities from GITT and EIS necessitates the precise computation of interfacial area, which gets even more complicated for NCM523 particle agglomerates exhibiting bimodal particle size distribution. Thus, it becomes imperative to design first an accurate mathematical descriptor of active area for NCM523 electrodes. This estimate is then coupled with macro homogeneous performance models to simulate GITT and half-cell performance of NCM523 electrodes. Refinement of the area estimates is execut...

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Learning from Overpotentials in Lithium Ion Batteries: A Case Study on the LiNi_1/3Co_1/3Mn_1/3O₂(NCM) Cathode

Cited by 123 publications

References 74 publications

Thermodynamic Model for Substitutional Materials: Application to Lithiated Graphite, Spinel Manganese Oxide, Iron Phosphate, and Layered Nickel-Manganese-Cobalt Oxide

Thermodynamic Model for Substitutional Materials: Application to Lithiated Graphite, Spinel Manganese Oxide, Iron Phosphate, and Layered Nickel-Manganese-Cobalt Oxide

Learning from Electrochemical Data: Simple Evaluation and Classification of LiMO₂‐type‐based Positive Electrodes for Li‐Ion Batteries

Galvanostatic Intermittent Titration and Performance Based Analysis of LiNi_0.5Co_0.2Mn_0.3O₂Cathode

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Learning from Overpotentials in Lithium Ion Batteries: A Case Study on the LiNi1/3Co1/3Mn1/3O2(NCM) Cathode

Cited by 123 publications

References 74 publications

Thermodynamic Model for Substitutional Materials: Application to Lithiated Graphite, Spinel Manganese Oxide, Iron Phosphate, and Layered Nickel-Manganese-Cobalt Oxide

Thermodynamic Model for Substitutional Materials: Application to Lithiated Graphite, Spinel Manganese Oxide, Iron Phosphate, and Layered Nickel-Manganese-Cobalt Oxide

Learning from Electrochemical Data: Simple Evaluation and Classification of LiMO2‐type‐based Positive Electrodes for Li‐Ion Batteries

Galvanostatic Intermittent Titration and Performance Based Analysis of LiNi0.5Co0.2Mn0.3O2Cathode

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Learning from Overpotentials in Lithium Ion Batteries: A Case Study on the LiNi_1/3Co_1/3Mn_1/3O₂(NCM) Cathode

Learning from Electrochemical Data: Simple Evaluation and Classification of LiMO₂‐type‐based Positive Electrodes for Li‐Ion Batteries

Galvanostatic Intermittent Titration and Performance Based Analysis of LiNi_0.5Co_0.2Mn_0.3O₂Cathode