Statistical mechanical modeling of the transition Stage II → Stage I of Li-ion storage in graphite. A priori vs induced heterogeneity

Otero, Manuel; Sigal, Agustín; Perassi, Eduardo Marcelo; Barraco, Daniel E.; Leiva, E.P.M.

doi:10.1016/j.electacta.2017.05.128

Cited by 16 publications

(25 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…g and Δ in this case. As shown in our previous work [2], the model results in well defined peaks, P1d/P1l and P2d/P2l in accordance with the ones obtained experimentally. We previously obtained values g = -0.45 kT and Δ = 1.12 kT, by comparing the simulation results with the experimental half widths and relative positions of the two peaks from slow rate cyclic voltammetry, Figure S1 This phenomenon is consistent with a density functional theory (DFT) study of Garay-Tapia et al [32], who showed that the binding energy of Li to graphene undergoes a rapid transition at low occupation, due to partial charge transfer from Li to the substrate.…”

Section: Thermodynamic Measurements Of Partial Molar Enthalpy and Entsupporting

confidence: 90%

“…However, its influence on the OCV is negligible, as shown in the inset of Figure 3. We used this model in our previous work to model lithium insertion in graphite [2,3] and, in a very similar form, lithium manganese oxide spinel with point defects [12]. All input parameters, along with their meaning and values are tabulated in Table 3.…”

Section: Thermodynamic Measurements Of Partial Molar Enthalpy and Entmentioning

confidence: 99%

“…To integrate this effect into our model, a larger number of available insertion sites, M, in each layer was required than our previous work [2,12], which only simulated P1l/P1d and P2l/P2d. This is Figure S7 for M = 150.…”

Section: Thermodynamic Measurements Of Partial Molar Enthalpy and Entmentioning

confidence: 99%

“…Recent theoretical work shows that some aspects of the behaviour of this material upon lithiation and delithiation still remain puzzling. For example, the role that the different stages formed play in the entropic behaviour of this material has been recently recognised, in terms of order/disorder transitions [1][2][3][4][5]. Furthermore, the understanding of the occurrence of defective (Daumas-Herold) structures on the basis of the kinetics of the lithium insertion process has also been reached in recent times [6][7][8].…”

Section: Introductionmentioning

confidence: 99%

“…In addition to fundamental understanding, these phenomena are important for achieving a cell level picture for practical applications such as battery management and aging. In our recent and ongoing work, we described order disorder transitions, including the Stage I-Stage II transition, through Grand Canonical Monte Carlo simulations [1,[9][10][11]] and a two level, mean field approach [2,12] . This transition is responsible for the main step in voltage with respect to lithium occupation (state of charge) that occurs close to 50 % lithiation in graphite.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Transitions of lithium occupation in graphite: A physically informed model in the dilute lithium occupation limit supported by electrochemical and thermodynamic measurements

Mercer

Otero

Ferrer-Huerta

et al. 2019

Electrochimica Acta

View full text Add to dashboard Cite

Understanding the role of the phase transitions during lithiation and delithiation of graphite remains a problem of fundamental importance, but also practical relevance owing to its widespread use as the anode material in most commercial lithium-ion cells. Previously performed density functional theory (DFT) calculations show a rapid change in the lithium-carbon interaction at low occupation, due to partial charge transfer from Li to C. We integrate this effect in our previously developed two level mean field model, which describes the Stage I-Stage II transition in graphite. The modified model additionally describes the most predominant transition that occurs at low Li content in graphite, which results in a previously unexplained feature in voltage and dQ/dV profiles, and thermodynamic measurements of partial molar enthalpy. In contrast with the Stage I-Stage II transition, this extra feature is not associated with observable features in the partial molar entropy and our model demonstrates why. There is a sharp change in the open circuit voltage at very low Li occupation, followed by a transition to a voltage plateau (peak in dQ/dV). The behaviour arises due to the contrasting effects of the partial molar entropy and enthalpy terms on the partial molar Gibbs energy and hence cell voltage. Hence the voltage profile and phase transitions can be approximated for all lithium occupations, potentially allowing a predictive capability in cell level models.

show abstract

Section: Thermodynamic Measurements Of Partial Molar Enthalpy and Entsupporting

confidence: 90%

Section: Thermodynamic Measurements Of Partial Molar Enthalpy and Entmentioning

confidence: 99%

Section: Thermodynamic Measurements Of Partial Molar Enthalpy and Entmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Transitions of lithium occupation in graphite: A physically informed model in the dilute lithium occupation limit supported by electrochemical and thermodynamic measurements

Mercer

Otero

Ferrer-Huerta

et al. 2019

Electrochimica Acta

View full text Add to dashboard Cite

show abstract

P‐Doped Ni/NiO Heterostructured Yolk‐Shell Nanospheres Encapsulated in Graphite for Enhanced Lithium Storage

Zhang

Chen

et al. 2021

Small

View full text Add to dashboard Cite

The development of high‐efficiency lithium‐ion battery electrodes composed of recycled materials is crucial for the commercialization of retired batteries, but it remains a significant barrier. The usage and recycling of spent graphite are encouraged by the huge number of batteries that are going to be dismantled. Here, an anode made of phosphorus‐doped Ni/NiO yolk‐shell nanospheres embedded on wasted graphite is developed. Electroless deposition and a subsequent heat‐treatment procedure are used to make it in a methodical manner. The internal vacuum space of the nanospheres mitigates volume expansion and facilitates Li+ diffusion, whereas the embedded metallic Ni and conductive graphite layer expedite charge transfer. The optimal reusable composite electrode is ecologically benign and has high specific capacities (724 mAh g−1 at 0.1 A g−1) as well as outstanding cycle stability (500 cycles). The unusual 3D sandwich‐like arrangement with strong spent graphite, the yolk‐shell hetero‐structure, continuous electron/ion transport routes, and attractive structure stability all contribute to this degree of performance. Such a nanoscale design and engineering strategy not only provides a green recovery method for anode graphite, but also enlightens other nanocomposites to boost their lithium storage performance.

show abstract

Numerical simulations of cyclic voltammetry for lithium-ion intercalation in nanosized systems: finiteness of diffusion versus electrode kinetics

Gavilán-Arriazu

Mercer

Pinto

et al. 2020

J Solid State Electrochem

Self Cite

View full text Add to dashboard Cite

The voltammetric behavior of Li + intercalation/deintercalation in/from LiMn 2 O 4 thin films and single particles is simulated, supporting very recent experimental results. Experiments and calculations both show that particle size and geometry are crucial for the electrochemical response. A remarkable outcome of this research is that higher potential sweep rates, of the order of several millivolts per second, may be used to characterize nanoparticles by voltammetry sweeps, as compared with macroscopic systems. This is in line with previous conclusions drawn for related single particle systems using kinetic Monte Carlo simulations. The impact of electrode kinetics and finite space diffusion on the reversibility of the process and the finiteness of the diffusion in ion Li / LiMn 2 O 4 (de)intercalation is also discussed in terms of preexisting modeling.

show abstract

Statistical mechanical modeling of the transition Stage II → Stage I of Li-ion storage in graphite. A priori vs induced heterogeneity

Cited by 16 publications

References 34 publications

Transitions of lithium occupation in graphite: A physically informed model in the dilute lithium occupation limit supported by electrochemical and thermodynamic measurements

Transitions of lithium occupation in graphite: A physically informed model in the dilute lithium occupation limit supported by electrochemical and thermodynamic measurements

P‐Doped Ni/NiO Heterostructured Yolk‐Shell Nanospheres Encapsulated in Graphite for Enhanced Lithium Storage

Numerical simulations of cyclic voltammetry for lithium-ion intercalation in nanosized systems: finiteness of diffusion versus electrode kinetics

Contact Info

Product

Resources

About