Determination of the chemical diffusion coefficient of lithium ions in spherical Li[Ni0.5Mn0.3Co0.2]O2

Yang, Shuo; Wang, Xianyou; Yang, Xiukang; Bai, Yiming; Liu, Ziling; Shu, Hongbo; Wei, Qufu

doi:10.1016/j.electacta.2012.01.061

Cited by 115 publications

(78 citation statements)

References 35 publications

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“…Experiments done by Yang et al 22 also exhibit hysteresis in the open circuit potential dataset during charge and discharge. Structural changes and phase transition can contribute to hysteresis between charge and discharge OCPs.…”

Section: Resultsmentioning

confidence: 99%

“…y = 1) to the start of GITT voltage (3.0 V), while simultaneously acknowledging reference values available in literature. 22 Subsequent SOC values are calculated using the current pulse, duration, active material mass and theoretical capacity magnitudes (see Tables II and III). For the 100 pulse GITT data set, a current of 0.136 mA is applied for a duration of 10.95 minutes.…”

Section: Resultsmentioning

confidence: 99%

“…Close to the end of lithiation, shorter current pulses can be used to identify the state of charge. Use of 40 pulses each during charge and discharge has been demonstrated by Yang et al 22 The rest period between charge and discharge pulses is given so that the cell can equilibrate to open circuit conditions. Beyond a threshold rest time value, the cell voltage should become constant with time.…”

Section: Methodsmentioning

confidence: 99%

“…2 sc r pr [22] Agglomerate surface area computation requires summing up the contributions of the N p hemispherical primary elements and is given by,…”

Section: A3386mentioning

confidence: 99%

“…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. * * Electrochemical Society Member.…”

mentioning

confidence: 99%

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

Verma

Smith

Santhanagopalan

et al. 2017

J. Electrochem. Soc.

114

123

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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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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

“…2 sc r pr [22] Agglomerate surface area computation requires summing up the contributions of the N p hemispherical primary elements and is given by,…”

Section: A3386mentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

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

Verma

Smith

Santhanagopalan

et al. 2017

J. Electrochem. Soc.

114

123

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Suppressing High‐Current‐Induced Phase Separation in Ni‐Rich Layered Oxides by Electrochemically Manipulating Dynamic Lithium Distribution

et al. 2021

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cathode materials and improve their stability and energy density. [1,2] In particular, Ni-rich NCM (LiNi x Co y Mn 1−x−y O 2 , x > 0.5) is a promising cathode material with high reversible capacity and has been successfully implemented in commercial energy storage systems, such as mobile devices and electric vehicles. [1] For Ni-rich layered oxides, the whole reaction pathway has been described as proceeding through a series of isostructural hexagonal phases, conventionally labeled as H1, H2, and H3 phases depending on the depth of charge. [3,4] The fundamental difference between H1 and H2 is the Li-content-dependent in-plane structure in the Li layer. [3,5] Because of the structural similarities of these evolving phases during cycling, the solid solution reaction has been predicted to be a thermodynamically favorable reaction pathway by first-principle studies [6] and was also observed by operando X-ray diffraction (XRD) experiments at moderate cycling rates in Ni-rich layered oxides, such as LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) [7] and LiNi 0.8 Co 0.1 Mn 0.1 O 2 . [3,4] Homogeneous Li transport, characterized by solid solution behaviors, is considered to be advantageous for obtaining a long cycle lifetime. [8] However, in dynamic situations such as fast cycling, limited Li diffusivity can induce a heterogeneous Li distribution within Understanding the cycling rate-dependent kinetics is crucial for managing the performance of batteries in high-power applications. Although high cycling rates may induce reaction heterogeneity and affect battery lifetime and capacity utilization, such phase transformation dynamics are poorly understood and uncontrollable. In this study, synchrotron-based operando X-ray diffraction is performed to monitor the high-current-induced phase transformation kinetics of LiNi 0.6 Co 0.2 Mn 0.2 O 2 . The sluggish Li diffusion at high Li content induces different phase transformations during charging and discharging, with strong phase separation and homogeneous phase transformation during charging and discharging, respectively. Moreover, by exploiting the dependence of Li diffusivity on the Li content and electrochemically tuning the initial Li content and distribution, phase separation pathway can be redirected to solid solution kinetics at a high charging rate of 7 C. Finite element analysis further elucidates the effect of the Li-content-dependent diffusion kinetics on the phase transformation pathway. The findings suggest a new direction for optimizing fast-cycling protocols based on the intrinsic properties of the materials.

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Optimized Temperature Effect of Li‐Ion Diffusion with Layer Distance in Li(Ni_xMn_yCo_z)O₂ Cathode Materials for High Performance Li‐Ion Battery

Cui

Wei

Liu

et al. 2015

Advanced Energy Materials

192

135

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energy density, high voltage, and long cycle life. [ 2 ] As one of the most widely used cathode materials, LiNi x Mn y Co z O 2 (labeled as NMC) has been investigated extensively, due to their high reversible capacity, good environmental compatibility, and relatively high Li-ion diffusivity. In the previous works, different kinds of NMC materials with different content ratio of Ni, Co, and Mn have been developed, and their electrochemical properties have also been studied, such as Li(Ni 1/3 Mn 1/3 Co 1/3 ) O 2 (111), [ 3,4 ] Li(Ni 0.4 Mn 0.4 Co 0.2 )O 2 (442), [ 5 ] Li(Ni 0.42 Mn 0.42 Co 0.16 )O 2 (552), [ 6 ] Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 (532), [ 7 ] Li(Ni 0.6 Mn 0.2 Co 0.2 )O 2 (622), [ 8 ] and Li(Ni 0.7 Mn 0.15 Co 0.15 )O 2 (71515). [ 9 ] For example, Noh et al. compared the electrochemical properties including the Li-ion diffusion coeffi cient, capacity retention, and electrochemical stabilities (25 to 55 °C) of layered NMC cathode materials ((111), (532), (622), (71515), (811) and Li(Ni 0.85 Mn 0.075 Co 0.075 )O 2 ) at room temperature and found that the Ni content had a great infl uence on the electrochemical properties. [ 10 ] Solid phase diffusion coeffi cient ( D s ) is one of the most important parameters for the active materials of the LIBs, as it determines the charge and discharge rate capability directly. In particular, for high power density applications, fast Li-ion transport in cathode materials is a key factor and must be needed. As a result, many experimental and theoretical works have been devoted to investigating the Li-ion diffusion properties in layered cathode materials. [ 11,12 ] However, to the best of our knowledge, there is little work reported to study the relationship between the layer distance and kinetics of Li-ion diffusion in different temperatures of layered NMC cathode materials systematically, which is important for LIBs applied in multitemperature environments.At the same time, in order to measure D s accurately, many methods such as galvanostatic intermittent titration technique (GITT), [ 3,[13][14][15][16] potentiostatic intermittent titration technique (PITT), [ 14,17 ] electrochemical impedance spectroscopy, [ 18 ] and cyclic voltammetry [ 19 ] have been developed in the past decades. Although factors such as the inaccuracy of the assumptions, Understanding and optimizing the temperature effects of Li-ion diffusion by analyzing crystal structures of layered Li(Ni x Mn y Co z )O 2 (NMC) ( x + y + z = 1) materials is important to develop advanced rechargeable Li-ion batteries (LIBs) for multi-temperature applications with high power density. Combined with experiments and ab initio calculations, the layer distances and kinetics of Li-ion diffusion of LiNi x Mn y Co z O 2 (NMC) materials in different states of Li-ion de-intercalation and temperatures are investigatedsystematically. An improved model is also developed to reduce the system error of the "Galvanostatic Intermittent Titration Technique" with a correction of NMC particle size distribution. The Li-ion diff...

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Determination of the chemical diffusion coefficient of lithium ions in spherical Li[Ni0.5Mn0.3Co0.2]O2

Cited by 115 publications

References 35 publications

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

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

Suppressing High‐Current‐Induced Phase Separation in Ni‐Rich Layered Oxides by Electrochemically Manipulating Dynamic Lithium Distribution

Optimized Temperature Effect of Li‐Ion Diffusion with Layer Distance in Li(Ni_xMn_yCo_z)O₂ Cathode Materials for High Performance Li‐Ion Battery

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Determination of the chemical diffusion coefficient of lithium ions in spherical Li[Ni0.5Mn0.3Co0.2]O2

Cited by 115 publications

References 35 publications

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

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

Suppressing High‐Current‐Induced Phase Separation in Ni‐Rich Layered Oxides by Electrochemically Manipulating Dynamic Lithium Distribution

Optimized Temperature Effect of Li‐Ion Diffusion with Layer Distance in Li(NixMnyCoz)O2 Cathode Materials for High Performance Li‐Ion Battery

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

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

Optimized Temperature Effect of Li‐Ion Diffusion with Layer Distance in Li(Ni_xMn_yCo_z)O₂ Cathode Materials for High Performance Li‐Ion Battery