Li2SnO3 as a Cathode Material for Lithium-ion Batteries: Defects, Lithium Ion Diffusion and Dopants

Kuganathan, Navaratnarajah; Kordatos, Apostolos; Chroneos, Alexander

doi:10.1038/s41598-018-30554-y

Cited by 35 publications

(40 citation statements)

References 47 publications

(38 reference statements)

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“…The lowest intrinsic defect energy process was calculated to be the cation mixing (anti-site) in which Li and Al exchange their atomic positions. This defect was noted in various oxide materials experimentally and theoretically [37][38][39][40][41][42][43][44][45][46][47]. The primary reasons for this defect include experimental conditions for the preparation of as-prepared compounds and cycling of as-prepared materials particularly in battery applications.…”

Section: Crystal Structure Intrinsic Defect Processes and LI Diffusionmentioning

confidence: 98%

Atomistic Simulations of the Defect Chemistry and Self-Diffusion of Li-ion in LiAlO2

et al. 2019

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Lithium aluminate, LiAlO 2 , is a material that is presently being considered as a tritium breeder material in fusion reactors and coating material in Li-conducting electrodes. Here, we employ atomistic simulation techniques to show that the lowest energy intrinsic defect process is the cation anti-site defect (1.10 eV per defect). This was followed closely by the lithium Frenkel defect (1.44 eV per defect), which ensures a high lithium content in the material and inclination for lithium diffusion from formation of vacancies. Li self-diffusion is three dimensional and exhibits a curved pathway with a migration barrier of 0.53 eV. We considered a variety of dopants with charges +1 (Na, K and Rb), +2 (Mg, Ca, Sr and Ba), +3 (Ga, Fe, Co, Ni, Mn, Sc, Y and La) and +4 (Si, Ge, Ti, Zr and Ce) on the Al site. Dopants Mg 2+ and Ge 4+ can facilitate the formation of Li interstitials and Li vacancies, respectively. Trivalent dopants Fe 3+ , Ni 3+ and Mn 3+ prefer to occupy the Al site with exoergic solution energies meaning that they are candidate dopants for the synthesis of Li (Al, M) O 2 (M = Fe, Ni and Mn) compounds.Energies 2019, 12, 2895 2 of 10 Computational MethodsThe present computational study was based on classical pair-wise potential calculations to describe LiAlO 2 via the General Utility Lattice Program (GULP) code [23,24]. In the present approach, the total energy (lattice energy) is determined by long range (i.e., Coulombic) and short range [i.e., electron-electron repulsive and attractive intermolecular forces (van der Waals forces)]. The latter were modelled using Buckingham potentials (refer to the supplementary information). The van der Waals forces arising from the spontaneous formation of instantaneous dipoles are very important as the formation energy results are sensitive to those forces. The present modelling approach takes into the account of Van der Waals forces as a function of the interatomic distance (r) [23,24]. Two-body Buckingham potential mentioned in the supplementary information consists of two parts. The first part of the equation represents the Pauli repulsion (electron-electron) and the second part denotes the van der Waals interaction. Ionic positions and lattice parameters were relaxed using the Broyden-Fletcher-Goldfarb-Shanno (BFGS) algorithm [24]. Convergence criteria dictated that in relaxed configurations, forces on each atom was <0.001 eV/Å. To introduce point defects in the lattice we used the Mott-Littleton methodology [25] similarly to recent work [26][27][28]. It is established that although the present methodology may overestimate the defect formation enthalpies at the dilute limit, the trends will be unchanged [29]. In a thermodynamic perspective defect parameters can be described by comparing the real (i.e., defective) crystal to an isobaric or isochoric ideal (i.e., non-defective) crystal. Defect formation parameters can be interconnected through thermodynamic relations [30,31], with the present atomistic simulations corresponding to the isobaric parameters for the mig...

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Section: Crystal Structure Intrinsic Defect Processes and LI Diffusionmentioning

confidence: 98%

Atomistic Simulations of the Defect Chemistry and Self-Diffusion of Li-ion in LiAlO2

et al. 2019

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“…This suggests that there is a possibility of a small amount of Na on Ni sites (Na Ni ) and Ni on Na sites (Ni •• Na ). This defect has been identified theoretically as a most promising defect in a variety of oxide materials [31][32][33][34][35][36][37][38][39][40][41][42]. During the preparation of as-prepared battery materials and the charge-discharge process, the presence of this defect was noted [35,[56][57][58][59].…”

Section: Intrinsic Defect Processesmentioning

confidence: 95%

“…Divalent doping on the Ni site is a promising stratergy to introduce Na interstitials as explained in the equation 8. A similar stratergy was applied to Li, Na, and Mg-ion battery materials in our previous theoretical studies [36][37][38][39][40][41][42][43][44][45][46][47]. The solution of MO (M = Mg, Co, Fe, Ca, Sr and Ba) was considered using the following reaction:…”

Section: Solution Of Divalent Dopantsmentioning

confidence: 99%

“…Good structural stability was also noted for more than 20 cycles.As there is a limited number of experimental reports available in the literature, further understanding of this material is necessary to optimize its performance in Na-ion batteries. Computational studies at the atomistic level can provide information on intrinsic defect energetics, ion migration and dopant substitution [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48]. To the best of our knowledge, there is no work reported related to defect and diffusion properties of NaNiO 2 .…”

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Defect, Diffusion and Dopant Properties of NaNiO2: Atomistic Simulation Study

et al. 2019

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Sodium nickelate, NaNiO2, is a candidate cathode material for sodium ion batteries due to its high volumetric and gravimetric energy density. The use of atomistic simulation techniques allows the examination of the defect energetics, Na-ion diffusion and dopant properties within the crystal. Here, we show that the lowest energy intrinsic defect process is the Na-Ni anti-site. The Na Frenkel, which introduces Na vacancies in the lattice, is found to be the second most favourable defect process and this process is higher in energy only by 0.16 eV than the anti-site defect. Favourable Na-ion diffusion barrier of 0.67 eV in the ab plane indicates that the Na-ion diffusion in this material is relatively fast. Favourable divalent dopant on the Ni site is Co2+ that increases additional Na, leading to high capacity. The formation of Na vacancies can be facilitated by doping Ti4+ on the Ni site. The promising isovalent dopant on the Ni site is Ga3+.

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“…To the best of our knowledge, no theoretical work has been reported on the defects, diffusion, and dopants in ilmenite. In previous studies [22][23][24][25][26][27][28][29], defects have been modeled in a variety of ionic oxide materials using different simulation methods. This work uses classical simulation techniques to examine the energetics of intrinsic defects; Fe-ion diffusion; and solutions of RO (R = Ni, Zn, Co, Mn, Ca, Sr, and Ba), R 2 O 3 (R = Al, Mn, Ga, Sc, In, Yb, Y, Gd, and La), and RO 2 (R = Si, Ge, Sn, Zr, and Ce) in…”

Section: Introductionmentioning

confidence: 99%

Theoretical Modeling of Defects, Dopants, and Diffusion in the Mineral Ilmenite

et al. 2019

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The iron titanium oxide ilmenite (FeTiO3) is a technologically and economically important mineral in the industrial preparation of titanium-based pigments and spintronic devices. In this study, atomistic simulation techniques based on classical pair potentials are used to examine the energetics of the intrinsic and extrinsic defects and diffusion of Fe2+ ions in FeTiO3. It is calculated that the cation anti-site (Fe‒Ti) cluster is the most dominant defect, suggesting that a small amount of cations exchange their positions, forming a disordered structure. The formation of Fe Frenkel is highly endoergic and calculated to be the second most stable defect process. The Fe2+ ions migrate in the ab plane with the activation energy of 0.52 eV, inferring fast ion diffusion. Mn2+ and Ge4+ ions are found to be the prominent isovalent dopants at the Fe and Ti site, respectively. The formation of additional Fe2+ ions and O vacancies was considered by substituting trivalent dopants (Al3+, Mn3+, Ga3+, Sc3+, In3+, Yb3+, Y3+, Ga3+, and La3+) at the Ti site. Though Ga3+ is found to be the candidate dopant, its solution enthalpy is >3 eV, suggesting that the formation is not significant at operating temperatures.

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Li2SnO3 as a Cathode Material for Lithium-ion Batteries: Defects, Lithium Ion Diffusion and Dopants

Cited by 35 publications

References 47 publications

Atomistic Simulations of the Defect Chemistry and Self-Diffusion of Li-ion in LiAlO2

Atomistic Simulations of the Defect Chemistry and Self-Diffusion of Li-ion in LiAlO2

Defect, Diffusion and Dopant Properties of NaNiO2: Atomistic Simulation Study

Theoretical Modeling of Defects, Dopants, and Diffusion in the Mineral Ilmenite

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