Extended Chemical Flexibility of Cubic Anti-Perovskite Lithium Battery Cathode Materials

Lai, Kwing To; Antonyshyn, Iryna; Prots, Yurii; Valldor, Martin

doi:10.1021/acs.inorgchem.8b01850

Cited by 19 publications

(21 citation statements)

References 23 publications

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“…If the same amount of lithium is extracted, Li 2 Fe 0.9 Co 0.1 SO shows the lowest relative change of the lattice parameter a comparing to Li 2 Fe 0.9 Mn 0.1 SO and Li 2 FeSO, which may be a reason for the fact that this material outperforms the other two compositions studied here. On the other hand, the entire replacement of Fe by Co to the Li 2 CoSO compound leads to significant decrease of the specific capacity down to 70 mAh/g as it was found in work (Lai et al, 2018).…”

Section: Discussionmentioning

confidence: 53%

“…Afterward, the ampule with the pellet was put in an oven, heated up to 750 • C with a rate of 50 • C/h, kept there for 3 h, and immediately cooled down to room temperature by quenching it in melting ice. In general, the synthesis route was taken from the previous reports on antiperovskites (Lai et al, 2018;Gorbunov et al, 2020); however, some parameters were varied to optimize the quality of the obtained materials.…”

Section: Synthesis and Pxrd Analysismentioning

confidence: 99%

“…Recently reported compounds with the antiperovskite structure represent an interesting class of materials for possible application as cathodes in Li-ion batteries (Lai et al, 2017(Lai et al, , 2018Mikhailova et al, 2018;Gorbunov et al, 2020). Among the studied materials, Li 2 CoSO and Li 2 MnSO (Lai et al, 2018), Li 2 FeSO (Lai et al, 2017;Mikhailova et al, 2018) and Li 2 Fe 0.5 Mn 0.5 SO (Gorbunov et al, 2020), the Li 2 FeSO compound demonstrates the most promising characteristics in terms of specific electrochemical capacities during galvanostatic cycling and rate capability. Other materials mentioned above show much lower specific capacity values not exceeding 100 mAh/g after few cycles (Lai et al, 2018) and quite a poor cycling behavior in lithium cells (Gorbunov et al, 2020).…”

Section: Introductionmentioning

confidence: 99%

“…Among the studied materials, Li 2 CoSO and Li 2 MnSO (Lai et al, 2018), Li 2 FeSO (Lai et al, 2017;Mikhailova et al, 2018) and Li 2 Fe 0.5 Mn 0.5 SO (Gorbunov et al, 2020), the Li 2 FeSO compound demonstrates the most promising characteristics in terms of specific electrochemical capacities during galvanostatic cycling and rate capability. Other materials mentioned above show much lower specific capacity values not exceeding 100 mAh/g after few cycles (Lai et al, 2018) and quite a poor cycling behavior in lithium cells (Gorbunov et al, 2020). The structure of antiperovskites differs significantly from known tunnel-like (olivine) (Padhi et al, 1997), two-dimensional (α-NaFeO 2 ) (Demourgues Guerlou et al, 1993), three-dimensional (spinel LiMn 2 O 4 ) (Thackeray et al, 1983), or polyanionic NASICON-or LISICON-type structures (Bukun et al, 1998), commonly used as cathodes for Li-ion or Na-ion batteries.…”

Section: Introductionmentioning

confidence: 99%

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Studies of Li2Fe0.9M0.1SO Antiperovskite Materials for Lithium–Ion Batteries: The Role of Partial Fe2+ to M2+ Substitution

et al. 2021

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Cubic Li2Fe0.9M0.1SO antiperovskites with M–Co2+, or Mn2+ were successfully synthesized by a solid-state technique, and studied as cathode materials in Li-batteries. The influence of the Co, and Mn cation substitution of Fe in Li2FeSO on the resulting electrochemical performance was evaluated by galvanostatic cycling, while the reaction mechanism was explored by applying operando X-ray absorption and X-ray diffraction techniques using synchrotron radiation facilities. Even 10% Fe-substitution by these metals completely changes the structural behavior of the material upon Li-removal and insertion, in comparison to Li2FeSO. The Co-substitution significantly improves cyclability of the material at high current densities in comparison to the non-substituted material, reaching a specific capacity of 250 mAh/g at 1C current density. In contrast, the Mn-substitution leads to deterioration of the electrochemical performance because of the impeded kinetics, which may be caused by the appearance of a second isostructural phase due to formation of Jahn-Teller Mn3+ cations upon delithiation.

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Section: Discussionmentioning

confidence: 53%

Section: Synthesis and Pxrd Analysismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Studies of Li2Fe0.9M0.1SO Antiperovskite Materials for Lithium–Ion Batteries: The Role of Partial Fe2+ to M2+ Substitution

et al. 2021

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“…Recently, an anti-perovskite structured oxysulphide Li 2 FeSO (Pm3m) was synthesised and found to have reasonably good electrochemical performance with a theoretical cationic redox capacity of 223 mAh/g, and a voltage of 2.5 V against graphite electrodes 22,23 . A subsequent computational study suggests that the anti-perovskite framework provides low lithium-diffusion barriers, and substituting Fe with other transition metal ions could lead to improved performance 24 .…”

Section: Introductionmentioning

confidence: 99%

Predicting stable lithium iron oxysulphides for battery cathodes

Zhu

Scanlon

2021

Preprint

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Cathode materials that have high specific energies and low manufacturing costs are vital for the scaling up of lithium-ion batteries (LIBs) as energy storage solutions. Fe-based intercalation cathodes are highly attractive because of the low-cost and the abundance of the raw materials. However, existing Fe-based materials, such as LiFePO 4 suffer from low capacity due to the large size of the polyanions. Turning to mixed anion systems can be a promising strategy to achieve higher specific capacity. Recently, anti-perovskite structured oxysulphide Li 2 FeSO has been synthesised and reported to be electrochemically active. In this work, we perform an extensive computational search for ironbased oxysulphides using ab initio random structure searching (AIRSS). By performing an unbiased sampling of the Li-Fe-S-O chemical space, several new oxysulphide phases have been discovered which are predicted to be less than 50 meV/atom from the convex hull and potentially accessible for synthesis. Among the predicted phases, two anti-Ruddlesden-Popper structured materials Li 2 Fe 2 S 2 O and Li 4 Fe 3 S 3 O 2 have been found to be attractive as they have high theoretical capacities with calculated average voltages 2.9 V and 2.5 V respectively. With band gaps as low as about 2.0 eV, they are expected to exhibit good electronic conductivities. By performing nudged-elastic band calculations, we show that the Li-ion transport in these materials takes place by hopping between the nearest neighbouring sites with low activation barriers between 0.3 eV and 0.5 eV. The richness of new materials yet to be synthesised in the Li-Fe-S-O phase field illustrates the great opportunity in these mixed anion systems for energy storage applications and beyond. LiFePO 43 , all of which were first proposed more than two decades ago. Iron-based cathode materials are very attractive as Fe is one of the most abundant transition metal in the upper crust with very low production costs. LIBs with olivine LiFePO 4 cathodes

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Cation Disordered Anti‐Perovskite Cathode Materials with Enhanced Lithium Diffusion and Suppressed Phase Transition

Deng

Chen

et al. 2023

Advanced Energy Materials

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Recently, a new family of anti‐perovskite Li2TMSO was discovered as promising cathode materials for Li‐ion batteries (LIBs) with superiorities in high specific capacity, low cost, and environmental friendliness. However, the applications of these anti‐perovskite materials meet severe challenges in the cyclability and rate performance. Herein, a cation‐disordered anti‐perovskite type solid solution Li2Fe1−xMnxSO (LFMSO, x = 0, 0.2, 0.5) with excellent electrochemical performance is reported. On the basis of comprehensive structural characterizations, the role of the cation disordering in LFMSO is clarified. In comparison with Li2FeSO (LFSO), the reduced Li‐ion diffusion barrier and the increased Li‐rich octahedral configurations in LFMSO with higher configurational entropy imply the facilitated long‐range Li‐ion diffusion and the suppressed phase transition, which favor the high‐rate capability and cycling stability. In addition, the large lattice distortion and Coulombic interaction between the anions and cations lead to the breathing of the unit cell during charge/discharge. The variation of the unit cell volume decreases to 2.5% upon Li‐ion delithiation. A superstructure is observed in LFMSO for the first time. These findings help to pave the way for the research and development of novel cathode materials for the next generation LIBs.

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Extended Chemical Flexibility of Cubic Anti-Perovskite Lithium Battery Cathode Materials

Cited by 19 publications

References 23 publications

Studies of Li2Fe0.9M0.1SO Antiperovskite Materials for Lithium–Ion Batteries: The Role of Partial Fe2+ to M2+ Substitution

Studies of Li2Fe0.9M0.1SO Antiperovskite Materials for Lithium–Ion Batteries: The Role of Partial Fe2+ to M2+ Substitution

Predicting stable lithium iron oxysulphides for battery cathodes

Cation Disordered Anti‐Perovskite Cathode Materials with Enhanced Lithium Diffusion and Suppressed Phase Transition

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