Nanostructured Zn Mn3‒O4 thin films by pulsed laser deposition: A spectroscopic and electrochemical study towards the application in aqueous Zn-ion batteries

Macrelli, Andrea; Olivieri, Marco; Lamperti, Alessio; Russo, Valeria; Bozzini, Benedetto; Menegazzo, Marco; Bussetti, Gianlorenzo; Casari, Carlo Spartaco; Bassi, Andrea

doi:10.1016/j.electacta.2023.141909

Cited by 3 publications

(3 citation statements)

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“…The morphology of the as-deposited MnO x thin films is depicted in the top-view and cross-sectional SEM images of Figure a,b;c,d for the samples grown at 1 and 10 Pa of O 2 , respectively. As expected with PLD-grown oxides − and in agreement with our previous work about MnO x thin films, the film nanoscale morphology is deeply affected by the O 2 deposition partial pressure. Indeed, a compact and nearly smooth surface is observed in the film grown at 1 Pa (Figure a), with weakly visible features corresponding to the surface facets of nanocrystalline structures constituting the film.…”

Section: Resultssupporting

confidence: 91%

Probing the Annealing-Induced Phase Evolution of Nanostructured Manganese Oxide Thin Films by X-Ray Diffraction

Macrelli,

Lamperti,

Dellasega

et al. 2024

Crystal Growth & Design

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Nanostructured manganese oxide thin films with different crystallinity and nanomorphology were synthesized by pulsed laser deposition (PLD) in oxygen gas. Through grazing-incidence X-ray diffraction during postdeposition thermal annealing in oxidizing (air) or inert (N 2 flux) atmospheres, phase changes, crystallization onsets, and orientation effects were evaluated between room temperature and 600 °C, revealing a significant impact of growth conditions and nanoscale morphology on the X-ray patterns. Compact nanocrystalline Mn 3 O 4 films underwent first crystallization improvement between 300 and 485 °C accompanied by unit cell shrinkage, then phase transition to α-Mn 2 O 3 above 500 °C in an oxidizing environment. In contrast, during annealing under N 2 flux, crystalline Mn 3 O 4 was stable up to 600 °C, maintaining the preferential orientation promoted by PLD. Similarly, nanoporous amorphous MnO 2 films crystallized to α-Mn 2 O 3 (>480 °C) and Mn 3 O 4 (∼385 °C) in oxidizing and inert atmospheres, respectively; however, the amorphous porous morphology led to poorer crystallinity and an isotropic, powder-like crystal orientation. Quantitative analysis of structural parameters in the whole temperature range and microscopic and Raman analyses complemented the results. These findings shed light on the structural stability and nanoscale design achievable by PLD, followed by suitable annealing, of materials relevant for several technological applications.

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Section: Resultssupporting

confidence: 91%

Probing the Annealing-Induced Phase Evolution of Nanostructured Manganese Oxide Thin Films by X-Ray Diffraction

Macrelli,

Lamperti,

Dellasega

et al. 2024

Crystal Growth & Design

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“…MnOx thin films were grown on silicon (100) substrates (Siegert Wafer) by PLD, using an experimental apparatus already described elsewhere [38,39]. Briefly, a MnO vacuum hot-pressed target (99.9% purity, Testbourne B.V.) was ablated by nanosecond laser pulses from a Nd:YAG laser source (2 nd harmonic, λ=532 nm, repetition rate 10 Hz, pulse duration 5-7 ns).…”

Section: A Synthesis Of Mnox Thin Filmsmentioning

confidence: 99%

Nanostructure and phase engineering of manganese oxide thin films grown by pulsed laser deposition: A Raman and XRD study

Macrelli,

Monforte Ferrario,

Lamperti

et al. 2023

Phys. Rev. Materials

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Manganese, showing stable oxidation states spanning from +2 to +7, gives rise to a variety of oxides (MnOx) whose exploitation in several technological fields, such as energy conversion and storage, catalysis, sensing, environmental and biomedical engineering, is highly promising. Nevertheless, the chemical complexity and the structural richness of MnOx -involving mixed-valence and metastable species -make the correct identification by Raman spectroscopy challenging, further complicated by the laser sensitivity, the poor Raman activity, and the conflicting literature scenario. Moreover, a careful optimization of the material in terms of phase, structure, and morphology is highly desirable in view of the final application, where a precise control over the materials properties is essential. In this work, we discuss the capability of room-temperature pulsed laser deposition (PLD), followed by post-deposition thermal treatments, to successfully grow engineered and pure MnOx thin films, whose phase and morphology at the nanoscale can be totally decoupled and independently optimized. The detailed Raman characterization of these films enabled a clear identification of specific MnOx phases and poses the basis for the rationale of the MnOx Raman spectra. Starting from the same MnO PLD target, we obtained five different MnOx phases (i.e., MnO, Mn3O4, Mn2O3, amorphous MnO2, and α-MnO2) with tailored and tunable degree of porosity and crystallinity, by modulating process parameters like the O2 deposition partial pressure (vacuum -100 Pa), the type of substrate, and the annealing temperature (300-900 °C) and atmosphere (air/vacuum). The Raman spectroscopy reliability of the MnOx phase assignment was assessed by thoroughly investigating the impact of the exciting laser power, and it was further validated by energy-dispersive X-ray spectroscopy, X-ray photoemission spectroscopy, and X-ray diffraction, providing additional insights into the compositional properties and the crystalline structure.

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“…At present, aqueous zinc ion batteries (AZIBs) have been widely studied for energy storage due to various advantages such as low cost, environmental benignity, and high safety performance [1][2][3][4][5][6][7][8][9][10]. So far, there have been various materials reported to be suitable as cathodes for AZIBs, including manganese-based materials [11][12][13][14][15], vanadium-based materials [16][17][18][19][20], and Prussian blue analogs [21][22][23][24].…”

Section: Introductionmentioning

confidence: 99%

An Artificial MnWO4 Cathode Electrolyte Interphase Enabling Enhanced Electrochemical Performance of δ-MnO2 Cathode for Aqueous Zinc Ion Battery

et al. 2023

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The dissolution of active material in aqueous batteries can lead to a rapid deterioration in capacity, and the presence of free water can also accelerate the dissolution and trigger some side reactions that affect the service life of aqueous batteries. In this study, a MnWO4 cathode electrolyte interphase (CEI) layer is constructed on a δ-MnO2 cathode by cyclic voltammetry, which is effective in inhibiting the dissolution of Mn and improving the reaction kinetics. As a result, the CEI layer enables the δ-MnO2 cathode to produce a better cycling performance, with the capacity maintained at 98.2% (vs. activated capacity at 500 cycles) after 2000 cycles at 10 A g−1. In comparison, the capacity retention rate is merely 33.4% for pristine samples in the same state, indicating that this MnWO4 CEI layer constructed by using a simple and general electrochemical method can promote the development of MnO2 cathodes for aqueous zinc ion batteries.

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Nanostructured Zn Mn3‒O4 thin films by pulsed laser deposition: A spectroscopic and electrochemical study towards the application in aqueous Zn-ion batteries

Cited by 3 publications

References 91 publications

Probing the Annealing-Induced Phase Evolution of Nanostructured Manganese Oxide Thin Films by X-Ray Diffraction

Probing the Annealing-Induced Phase Evolution of Nanostructured Manganese Oxide Thin Films by X-Ray Diffraction

Nanostructure and phase engineering of manganese oxide thin films grown by pulsed laser deposition: A Raman and XRD study

An Artificial MnWO4 Cathode Electrolyte Interphase Enabling Enhanced Electrochemical Performance of δ-MnO2 Cathode for Aqueous Zinc Ion Battery

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