Combined DFT and geometrical–topological analysis of Li-ion conductivity in complex hydrides

Gulino, Valerio; Wolczyk, Anna Roza; Golov, Andrey A.; Eremin, Roman A.; Palumbo, Mauro; Nervi, Carlo; Блатов, В. А.; Proserpio, Davide M.; Baricco, Marcello

doi:10.1039/d0qi00577k

Cited by 19 publications

(21 citation statements)

References 49 publications

(64 reference statements)

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“…The so-obtained E a is equal to 0.29 ± 0.03 eV below 60 °C. The obtained E a is considerably lower than the average value reported in the literature for pure LiBH 4 (0.75 ± 0.07 eV), 41 but it is similar to values observed for other SSEs. 42 …”

Section: Results and Discussionsupporting

confidence: 83%

Room-Temperature Solid-State Lithium-Ion Battery Using a LiBH₄–MgO Composite Electrolyte

Gulino

Brighi

Murgia

et al. 2021

ACS Appl. Energy Mater.

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LiBH 4 has been widely studied as a solid-state electrolyte in Li-ion batteries working at 120 °C due to the low ionic conductivity at room temperature. In this work, by mixing with MgO, the Li-ion conductivity of LiBH 4 has been improved. The optimum composition of the mixture is 53 v/v % of MgO, showing a Li-ion conductivity of 2.86 × 10 –4 S cm –1 at 20 °C. The formation of the composite does not affect the electrochemical stability window, which is similar to that of pure LiBH 4 (about 2.2 V vs Li + /Li). The mixture has been incorporated as the electrolyte in a TiS 2 /Li all-solid-state Li-ion battery. A test at room temperature showed that only five cycles already resulted in cell failure. On the other hand, it was possible to form a stable solid electrolyte interphase by applying several charge/discharge cycles at 60 °C. Afterward, the battery worked at room temperature for up to 30 cycles with a capacity retention of about 80%.

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Section: Results and Discussionsupporting

confidence: 83%

Room-Temperature Solid-State Lithium-Ion Battery Using a LiBH₄–MgO Composite Electrolyte

Gulino

Brighi

Murgia

et al. 2021

ACS Appl. Energy Mater.

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“…The background was described through a polynomial function with 3 or 4 parameters. The following sequence was applied for the refinement of parameters: (1) scale factor (2) background parameters (3) lattice constants (4) crystallites size (5) micro-strain. In some cases, also the occupancy and the position of the 2b site in the hexagonal structure were refined.…”

Section: Rietveld Analysismentioning

confidence: 99%

“…3 In 2007, Matsuo et al 4 reported a drastic increase of the Li-ion conductivity of LiBH4 above the phase transition temperature, suggesting it as a solid-state electrolyte. Despite the hexagonal polymorph (h-LiBH4) shows a remarkable ionic conductivity (~10 −3 S cm -1 at 120 °C), the orthorhombic room temperature phase (o-LiBH4) is much less conductive, showing a Li-ion conductivity of 9.5 × 10 −9 ± 2 × 10 −9 S cm -1 at 30 °C, 5 making a room temperature battery target unviable. 4 Different approaches have been used to increase the Li-ion conductivity of LiBH4 at RT, such as by mixing it with oxides or by means of nanoconfinement.…”

Section: Introductionmentioning

confidence: 99%

Theoretical and Experimental Studies of LiBH₄–LiBr Phase Diagram

Gulino

Dematteis

Corno

et al. 2021

ACS Appl. Energy Mater.

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Because substitutions of BH4anion with Brcan stabilize the hexagonal structure of the LiBH4 at room temperature, leading to a high Li-ion conductivity, its thermodynamic stability has been investigated in this work. The binary LiBH4-LiBr system has been explored by means of X-ray diffraction and differential scanning calorimetry, combined with an assessment of thermodynamic properties. The monophasic zone of the hexagonal Li(BH4)1-x(Br)x solid solution has been defined equal to 0.30 ≤ x ≤ 0.55 at 30 °C. Solubility limits have been determined by in-situ X-ray diffraction at various temperatures. For the formation of the h-Li(BH4)0.6(Br)0.4 solid solution, a value of the enthalpy of mixing (∆Hmix) has been determined experimentally equal to -1.0 ± 0.2 kJ/mol,. In addition, the enthalpy of melting has been measured for various compositions. Lattice stabilities of LiBH4 and LiBr have been determined by ab initio calculations, using CRYSTAL and VASP codes.Combining results of experiments and theoretical calculations, the LiBH4-LiBr phase diagram has been determined in all composition and temperature range by the CALPHAD method.

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“…Previous studies have used few representative structures with distinct migration topologies to derive rules for the migration in multivalent magnesium battery materials [7,10] . Geometrical investigations in combination with cheaper computational methods based on Bond Valence Site Energies (BVSE) [11] or DFT calculations on a few selected structures [12] have been conducted. They discussed the importance of being able to describe the geometry of the transition state along the migration path in order to predict kinetic barriers.…”

Section: Introductionmentioning

confidence: 99%

Automatic Migration Path Exploration for Multivalent Battery Cathodes using Geometrical Descriptors

Bölle

Bhowmik

Vegge

et al. 2021

Batteries & Supercaps

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Stable and fast ionic conductors for magnesium cathode materials have the prospect of enabling high energy density batteries beyond current Lithium‐ion technologies. So far, only a few candidate materials have been identified leading to data only being scarcely available to the community. Here, we present a systematic study, in the framework of Density Functional Theory, including the estimation of the migration barrier for 16 materials through employing Nudged Elastic Band (NEB) calculations. By introducing a path finder algorithm based on the idea of Voronoi tessellations, we show that an estimate of the transition state configuration can be extracted automatically prior to running NEB‐calculations. Using geometrical descriptors in combination with a principal component analysis it is possible to further sub‐group the migration paths. This approach also extends to materials which are not part of the study, making it a viable approach to more efficiently explore crystal structures with distinguishable migration characteristics.

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Combined DFT and geometrical–topological analysis of Li-ion conductivity in complex hydrides

Abstract: On the basis of DFT calculations, the Li-ion migration was analyzed for LiBH4, LiNH2, Li2NH, Li2BH4NH2, Li4BH4(NH2)3 and Li5(BH4)3NH complex hydrides by means of the nudged elastic band method. In...

Cited by 19 publications

References 49 publications

Room-Temperature Solid-State Lithium-Ion Battery Using a LiBH₄–MgO Composite Electrolyte

Room-Temperature Solid-State Lithium-Ion Battery Using a LiBH₄–MgO Composite Electrolyte

Theoretical and Experimental Studies of LiBH₄–LiBr Phase Diagram

Automatic Migration Path Exploration for Multivalent Battery Cathodes using Geometrical Descriptors

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Combined DFT and geometrical–topological analysis of Li-ion conductivity in complex hydrides

Abstract: On the basis of DFT calculations, the Li-ion migration was analyzed for LiBH4, LiNH2, Li2NH, Li2BH4NH2, Li4BH4(NH2)3 and Li5(BH4)3NH complex hydrides by means of the nudged elastic band method. In...

Cited by 19 publications

References 49 publications

Room-Temperature Solid-State Lithium-Ion Battery Using a LiBH4–MgO Composite Electrolyte

Room-Temperature Solid-State Lithium-Ion Battery Using a LiBH4–MgO Composite Electrolyte

Theoretical and Experimental Studies of LiBH4–LiBr Phase Diagram

Automatic Migration Path Exploration for Multivalent Battery Cathodes using Geometrical Descriptors

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Product

Resources

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Room-Temperature Solid-State Lithium-Ion Battery Using a LiBH₄–MgO Composite Electrolyte

Room-Temperature Solid-State Lithium-Ion Battery Using a LiBH₄–MgO Composite Electrolyte

Theoretical and Experimental Studies of LiBH₄–LiBr Phase Diagram