Elucidating the electrochemical reaction mechanism of lithium-rich antiperovskite cathodes for lithium-ion batteries as exemplified by (Li<sub>2</sub>Fe)SeO

Singer, L.; Mohamed, Mostafa A.; Hahn, Henrik; González-Martínez, Ignacio; Hantusch, Martin; Wenelska, Karolina; Mijowska, Ewa; Büchner, B.; Hampel, Silke; Gräßler, Nico; Klingeler, R.

doi:10.1039/d3ta00552f

Cited by 4 publications

(9 citation statements)

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“…Specifically, the pair R 3 /O 3 in the low-voltage range which is attributed to the electrochemical activity of Fe 1–x S x increases drastically, while simultaneously, a significant decrease in the antiperovskite-associated oxidation processes (O 1 , O 2 , and O * ) is observed. Both the appearance of an extra feature as well as observed irreversibility is similar to what is found in (Li 2 Fe)SeO . We therefore conclude that during the anionic O* process, the antiperovskite phase decomposed and one or several iron sulfide phases are formed.…”

Section: Resultssupporting

confidence: 80%

“…In our recent works on (Li 2 Fe)SeO, we have demonstrated the stabilizing effect of selenium as an anion in the antiperovskite structure for the electrochemical performance . We have also shown that the poor cycling stability in this system originates from the high-voltage electrochemical processes causing decomposition of the antiperovskite structure . When cutting off the decomposition reaction, the cycle stability is significantly improved (over 80% capacity retention after 100 cycles for (Li 2 Fe)SeO at 1 C in the voltage range from 1 to 2.5 V) .…”

Section: Introductionmentioning

confidence: 88%

“…The recent discovery of the lithium-rich antiperovskite compounds characterized by the general formula (Li 2 TM)ChO (with TM = Fe, Mn, Co; Ch = S, Se) has significantly broadened the landscape of potential cathode materials for lithium-ion batteries (LIBs) . This novel class of materials showcases highly favorable attributes in the context of lithium-ion battery application, including cost effectiveness, utilization of environmentally benign raw materials, efficient lithium diffusion, and the ability of multielectron storage per chemical unit. − From the so far investigated antiperovskite materials Li 2 FeSO, ,,− (Li 2 Co)SO, (Li 2 Mn)SO, (Li 2 Fe 1– x Mn x )SO, ,, (Li 2 Fe 0.9 Co 0.1 )SO, (Li 2 Co)SeO, (Li 2 Mn)SeO, (Li 2 Fe)S 1– x Se x O, and (Li 2 Fe)SeO, ,, the (Li 2 Fe)SO compound captivates with the highest theoretical capacity. Despite the promises of lithium-rich antiperovskites and especially (Li 2 Fe)SO, their great potential could not be fully exploited due to poor cycling stability (only 66% capacity retention in (Li 2 Fe)SO at 0.1 C after 50 cycles) …”

Section: Introductionmentioning

confidence: 99%

“…Optimized (Li 2 Fe)SO exhibits a high capacity of around 175 mAh g –1 , which only marginally decreases by less than 4% over 100 cycles at 1 C if the electrochemical processes are restrained to only the cationic processes. Including the anionic processes yields after a few cycles twice this capacity, but severe fading by more than 75% (typical for Li-rich antiperovskites ,, ) displays that this process is detrimental for cycling stability. Our results further unveil that particle size is not a key parameter for electrochemical performance in Li-rich antiperovskites, but impurities present in the samples govern the observed differences.…”

Section: Introductionmentioning

confidence: 99%

“…17 We have also shown that the poor cycling stability in this system originates from the high-voltage electrochemical processes causing decomposition of the antiperovskite structure. 14 When cutting off the decomposition reaction, the cycle stability is significantly improved (over 80% capacity retention after 100 cycles for (Li 2 Fe)SeO at 1 C in the voltage range from 1 to 2.5 V). 14 A big challenge to further improve the cycling stability in (Li 2 Fe)SeO is however the clear separation of the second step of the cationic two-stage iron oxidation reaction from the highly overlapping anionic decomposition reaction.…”

Section: Introductionmentioning

confidence: 99%

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Separating Cationic and Anionic Redox Activity in the Lithium-Rich Antiperovskite (Li₂Fe)SO

Singer,

Dong,

Mohamed

et al. 2024

ACS Appl. Mater. Interfaces

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Lithium-rich antiperovskites promise to be a compelling class of high-capacity cathode materials due to the existence of both cationic and anionic redox activity. Little is however known about the effect of separating the electrochemical cationic process from the anionic process and the associated implications on the electrochemical performance. In this context, we report the electrochemical properties of the illustrative example of three different (Li 2 Fe)SO materials with a focus on separating cationic from anionic effects. With the high-voltage anionic process, an astonishing electrochemical capacity of around 400 mAh g −1 can initially be reached. Our results however identify the anionic process as the cause of poor cycling stability and demonstrate that the fading reported in previous literature is avoided by restricting to only the cationic processes. Following this path, our (Li 2 Fe)SO-BM500 shows strongly improved performance as indicated by constant electrochemical cycling over 100 cycles at a capacity of around 175 mAh g −1 at 1 C. Our approach also allows us to investigate the electrochemical performance of the bare antiperovskite phase excluding extrinsic activity from initial or cycling-induced impurity phases. Our results underscore that synthesis conditions are a critical determinant of electrochemical performance in lithium-rich antiperovskites, especially with regard to the amount of electrochemical secondary phases, while the particle size has not been found to be a crucial parameter. Overall, separating and understanding the effects of the cationic from the anionic redox activity in lithium-rich antiperovskites provides the route to further improve their performance in electrochemical energy storage.

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Section: Resultssupporting

confidence: 80%

Section: Introductionmentioning

confidence: 88%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Separating Cationic and Anionic Redox Activity in the Lithium-Rich Antiperovskite (Li₂Fe)SO

Singer,

Dong,

Mohamed

et al. 2024

ACS Appl. Mater. Interfaces

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Insights on Prussian Blue Analogue Cathode Material Engineered with Polypyrrole Surface Protection Layer for Aqueous Rechargeable Zinc Metal Battery

Puthiyaveetil,

Nair,

Dilwale

et al. 2024

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One of the key intricacies against using Prussian blue analogues (PBAs) in aqueous batteries is their gradual dissolution in aqueous electrolytes, resulting in inadequate cycling stability. Besides, the rate capability of PBAs is limited due to their poor electrical conductivity. To overcome these challenges, it is essential to tune the physical and chemical properties of PBAs at the nano regime without affecting the inherent charge storage properties, especially at high‐voltage operating conditions. Through this work, a strategy is demonstrated to enhance the electrochemical performance of vanadium‐based PBA (V‐PBA) by surface engineering using a conducting polymer nano‐skin (V‐PBA/PPy) for aqueous zinc metal batteries. The polypyrrole (PPy) nano‐skin over the V‐PBA nanoparticles acts as an electron percolation path to ameliorate the poor electronic conductivity of the otherwise pristine V‐PBA. Interestingly, the V‐PBA with an optimized polypyrrole coating (V‐PBA/PPy‐2) exhibits an enhanced specific capacity (173 mAh g−1 at 0.10 A g−1) than the pristine V‐PBA counterpart (80 mAh g−1) and 85% capacity retention up to 500 cycles. The DFT calculation confirms the synergistic interaction between PPy and V‐PBA and the presence of PPy favors the adsorption of Zn.

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Antiperovskite active materials for metal-ion batteries: Expected advantages, limitations, and perspectives

Dai,

Kouoi,

Reynaud

et al. 2024

Energy Storage Materials

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Elucidating the electrochemical reaction mechanism of lithium-rich antiperovskite cathodes for lithium-ion batteries as exemplified by (Li₂Fe)SeO

Abstract: We report outstanding properties of the antiperovskite cathode material (Li2Fe)SeO which for the first time was synthesized via direct ball-milling. The unique structured material displays excellent electrochemical cycling performance of...

Cited by 4 publications

References 37 publications

Separating Cationic and Anionic Redox Activity in the Lithium-Rich Antiperovskite (Li₂Fe)SO

Separating Cationic and Anionic Redox Activity in the Lithium-Rich Antiperovskite (Li₂Fe)SO

Insights on Prussian Blue Analogue Cathode Material Engineered with Polypyrrole Surface Protection Layer for Aqueous Rechargeable Zinc Metal Battery

Antiperovskite active materials for metal-ion batteries: Expected advantages, limitations, and perspectives

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Elucidating the electrochemical reaction mechanism of lithium-rich antiperovskite cathodes for lithium-ion batteries as exemplified by (Li2Fe)SeO

Abstract: We report outstanding properties of the antiperovskite cathode material (Li2Fe)SeO which for the first time was synthesized via direct ball-milling. The unique structured material displays excellent electrochemical cycling performance of...

Cited by 4 publications

References 37 publications

Separating Cationic and Anionic Redox Activity in the Lithium-Rich Antiperovskite (Li2Fe)SO

Separating Cationic and Anionic Redox Activity in the Lithium-Rich Antiperovskite (Li2Fe)SO

Insights on Prussian Blue Analogue Cathode Material Engineered with Polypyrrole Surface Protection Layer for Aqueous Rechargeable Zinc Metal Battery

Antiperovskite active materials for metal-ion batteries: Expected advantages, limitations, and perspectives

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Elucidating the electrochemical reaction mechanism of lithium-rich antiperovskite cathodes for lithium-ion batteries as exemplified by (Li₂Fe)SeO

Separating Cationic and Anionic Redox Activity in the Lithium-Rich Antiperovskite (Li₂Fe)SO

Separating Cationic and Anionic Redox Activity in the Lithium-Rich Antiperovskite (Li₂Fe)SO