Proton intercalation into different CoO2 layer matrices

Medina, Elena A.; Aleksandrova, Irina; Karppinen, Maarit

doi:10.1016/j.jssc.2019.120899

Cited by 9 publications

(25 citation statements)

References 43 publications

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“…As illustrated in Figure , one structure containing an equimolar concentration of Na + and H + was predicted to be stable. The simultaneous presence of both species in the P2-type structure agrees with H + insertion experiments for the P2-Na x CoO 2 material . The structures with higher energy above hull are located in the central region of the phase diagram, where the concentration of vacancies, Na + , and H + is similar.…”

Section: Resultssupporting

confidence: 80%

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Influence of Stacking on H⁺ Intercalation in Layered ACoO₂ (A = Li, Na) Cathode Materials and Implications for Aqueous Li-Ion Batteries: A First-Principles Investigation

2021

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Li- and Na-ion batteries are effective energy storage technologies. Nonetheless, currently used organic-electrolyte batteries present well-known safety problems. Therefore, the research community is intensively looking for potential alternatives. Aqueous batteries based on low-cost salts in water could be an interesting choice since they are safe and environmentally benign. However, working with aqueous electrolytes brings new detrimental mechanisms such as proton intercalation. Understanding the (de)intercalation chemistry of protons and alkali is one of the keys for designing cathode materials in such aqueous electrochemical cells. In this work, we carry out density functional theory calculations to investigate the H+/alkali exchange in layered LiCoO2 and NaCoO2 materials. By computing the grand potential phase diagram and voltage–composition plots, we determine the relative stability of several orderings of protons, alkali, and vacancies. The fully protonated CoO2 lattice (CoO(OH)) is revealed to be the most stable insertion product due to the formation of interlayer hydrogen bonds. Our computations demonstrate the key role of layer stacking: H+ insertion is favored in prismatic (P) stacking, while Li favors octahedral (O) stacking. While the fully protonated layered cobalt oxide is the thermodynamically favored product when protons and alkali compete, we show that mixing protons and lithium is energetically disfavored because of the different stacking preferences. We suggest that the kinetic difficulty in nucleating fully protonated phases in the layered oxide prevents proton insertion when cycling LiCoO2 in an aqueous electrolyte. The good cyclability and lack of proton insertion in LiCoO2 are, therefore, a result of the slow kinetics of protonation in partially lithiated cobalt oxide. On the other hand, we demonstrate that NaCoO2 is prone to proton and alkali mixing due to the different stacking preferences for sodium. We hypothesize that this could lead to proton intercalation and poor performances in aqueous batteries for NaCoO2 cathodes.

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Section: Resultssupporting

confidence: 80%

“…We hypothesize that the difficulty in mixing H + and Li + in the same structure (due to their very different stacking preferences) requires the nucleation of large fully protonated regions, a process that is likely to be difficult kinetically. It can justify the slow H + /Li + detected in hydrothermal experiments …”

Section: Resultsmentioning

confidence: 71%

Influence of Stacking on H⁺ Intercalation in Layered ACoO₂ (A = Li, Na) Cathode Materials and Implications for Aqueous Li-Ion Batteries: A First-Principles Investigation

2021

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“…[73] After the solvent reaction process, the phase transition from NaFeAs to NaFe 2 As 2 occurred (Figure 7e), leading to the production of a different crystal structure. The SAED pattern clearly confirmed that the Fe 2 As 2 layer shrunk compared to the FeAs layer in both zone axis [001] and [112]. Since 222 reflection is more split than 22 0, the lattice parameter along the c direction shrank more than that in the a and b directions (Figure 7f,g).…”

Section: Transmission Electron Microscopy/scanning Transmission Electron Microscopymentioning

confidence: 81%

“…H 2 O molecules in the interlayer spaces act as crystal water, behaving as atoms. [71,92,112] Thus, the existence of H 2 O molecules in the layers is expected to be governed by various factors such as the location of water, structure of the layers, and interaction between layers and H 2 O molecules. These factors themselves depend on the composition of the ABX compound.…”

Section: Solvent Reactionmentioning

confidence: 99%

“…e) Structure models of NaFeAs and NaFe 2 As 2 synthesized via solvent reaction. f,g) Electron diffraction patterns of NaFeAs and 3 h water-treated (green) NaFeAs samples along the zone axis [001] and [112], respectively. The insets, which are enlarged images of the boxed regions, clearly show the spot splits that indicate the cell contraction of the water-treated sample.…”

Section: Raman Spectroscopymentioning

confidence: 99%

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Kinetic 2D Crystals via Topochemical Approach

et al. 2021

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The designing of novel materials is a fascinating and innovative pathway in materials science. Particularly, novel layered compounds have tremendous influence in various research fields. Advanced fundamental studies covering various aspects, including reactants and synthetic methods, are required to obtain novel layered materials with unique physical and chemical properties. Among the promising synthetic techniques, topochemical approaches have afforded the platform for widening the extent of novel 2D materials. Notably, the synthesis of binary layered materials is considered as a major scientific breakthrough after the synthesis of graphene as they exhibit a wide spectrum of material properties with varied potential applicability. In this review, a comprehensive overview of the progress in the development of metastable layered compounds is presented. The various metastable layered compounds synthesized from layered ternary bulk materials through topochemical approaches are listed, followed by the descriptions of their mechanisms, structural analyses, characterizations, and potential applications. Finally, an essential research direction concerning the synthesis of new materials is indicated, wherein the possible application of topochemical approaches in unprecedented areas is explored.

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Unlocking the limitations of layered LiNiO2: Insights from DFT simulations on its viability as a cathode material for aqueous Lithium-ion batteries

George,

Brotons-Rufes,

Poater

et al. 2025

Journal of Power Sources

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Proton intercalation into different CoO2 layer matrices

Cited by 9 publications

References 43 publications

Influence of Stacking on H⁺ Intercalation in Layered ACoO₂ (A = Li, Na) Cathode Materials and Implications for Aqueous Li-Ion Batteries: A First-Principles Investigation

Influence of Stacking on H⁺ Intercalation in Layered ACoO₂ (A = Li, Na) Cathode Materials and Implications for Aqueous Li-Ion Batteries: A First-Principles Investigation

Kinetic 2D Crystals via Topochemical Approach

Unlocking the limitations of layered LiNiO2: Insights from DFT simulations on its viability as a cathode material for aqueous Lithium-ion batteries

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Proton intercalation into different CoO2 layer matrices

Cited by 9 publications

References 43 publications

Influence of Stacking on H+ Intercalation in Layered ACoO2 (A = Li, Na) Cathode Materials and Implications for Aqueous Li-Ion Batteries: A First-Principles Investigation

Influence of Stacking on H+ Intercalation in Layered ACoO2 (A = Li, Na) Cathode Materials and Implications for Aqueous Li-Ion Batteries: A First-Principles Investigation

Kinetic 2D Crystals via Topochemical Approach

Unlocking the limitations of layered LiNiO2: Insights from DFT simulations on its viability as a cathode material for aqueous Lithium-ion batteries

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Product

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Influence of Stacking on H⁺ Intercalation in Layered ACoO₂ (A = Li, Na) Cathode Materials and Implications for Aqueous Li-Ion Batteries: A First-Principles Investigation

Influence of Stacking on H⁺ Intercalation in Layered ACoO₂ (A = Li, Na) Cathode Materials and Implications for Aqueous Li-Ion Batteries: A First-Principles Investigation