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Search Results (1,098)

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13 pages, 7935 KiB  
Article
Future Parabolic Trough Collector Absorber Coating Development and Service Lifetime Estimation
by Ana Drinčić, Luka Noč, Franci Merzel and Ivan Jerman
Coatings 2024, 14(9), 1111; https://doi.org/10.3390/coatings14091111 - 2 Sep 2024
Viewed by 337
Abstract
This work presents a study on the optical and mechanical degradation of parabolic trough collector absorber coatings produced through the spray coating application technique of in-house developed paint. The main aim of this investigation is to prepare, cure, load, and analyze the absorber [...] Read more.
This work presents a study on the optical and mechanical degradation of parabolic trough collector absorber coatings produced through the spray coating application technique of in-house developed paint. The main aim of this investigation is to prepare, cure, load, and analyze the absorber coating on the substrate under conditions that mimic the on-field thermal properties. This research incorporates predicted isothermal and cyclic loads for parabolic trough systems as stresses. Biweekly inspections of loaded, identical samples monitored the degradation process. We further used the cascade of data from optical, oxide-thickening, crack length, and pull-off force measurements in mathematical modelling to predict the service life of the parabolic trough collector. The results collected and used in modelling suggested that cyclic load in combination with iso-thermal load is responsible for coating fatigue, influencing the solar absorber optical values and resulting in lower energy transformation efficiency. Finally, easy-to-apply coatings made out of spinel-structured black pigment and durable binder could serve as a low-cost absorber coating replacement for a new generation of parabolic trough collectors, making it possible to harvest solar energy to provide medium-temperature heat to decarbonize future food, tobacco, and paint production industrial processes. Full article
(This article belongs to the Special Issue Coatings for Advanced Devices)
Show Figures

Figure 1

Figure 1
<p>Schematic presentation of thermal load that simulates the on-field stress.</p>
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<p>Optical microscopy images for pigmented coatings as a function of time under thermal load at 300 °C after (<b>a</b>) initial application; (<b>b</b>) 2 weeks; (<b>c</b>) 4 weeks; (<b>d</b>) 6 weeks.</p>
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<p>Cross-cut of coating SEM/EDS image after 591 h at 400 °C.</p>
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<p>Oxide thickness as a function of time for different isothermal and cyclic loads.</p>
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<p>Dolly surface after pull-off test photos for samples after 1314 h under different thermal loads.</p>
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<p>Pull-off force as a function of loading time.</p>
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<p>Dependence of coating thickness on solar absorptance and thermal emittance values.</p>
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<p>Reflectance spectra of coatings with B444 pigment before thermal ageing and after 14 weeks (red and blue) at 300 °C. The orange spectrum represents pigmented coating on polished surface, which is close to the ideal spectrally selective coating (dashed line). In addition, graphs for blackbody radiation at 600 °C (violet) and AM 1.5 reference solar spectra (grey) are shown.</p>
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<p>Solar absorptance as a function of time after the isothermal thermal load for coatings made out of pigments.</p>
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<p>XRD spectra of the substrate and coated samples after one week of isothermal testing at 300, 400, and 500 °C in air furnace.</p>
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<p>Model degradation curve for solar absorptance as a function of time on the field (same load); threshold value is marked with red line.</p>
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21 pages, 20552 KiB  
Article
Fabrication of Co-Based Cladding Layer by Microbeam Plasma and Its Corrosion Mechanism to Molten Salt
by Kaiqi Sun, Yufeng Zhang, Yingfan Wang and Fuxing Ye
Materials 2024, 17(17), 4249; https://doi.org/10.3390/ma17174249 - 28 Aug 2024
Viewed by 346
Abstract
Corrosion of the molten salts Na2SO4 and NaCl has become one of the major factors in the failure of steel components in boilers and engines. In this study, CoNiCrAlY cobalt-based cladding layers with different NiCr-Cr3C2 ratios were [...] Read more.
Corrosion of the molten salts Na2SO4 and NaCl has become one of the major factors in the failure of steel components in boilers and engines. In this study, CoNiCrAlY cobalt-based cladding layers with different NiCr-Cr3C2 ratios were prepared by microbeam plasma cladding technology. The influence of the NiCr-Cr3C2 content on the microstructure, mechanical properties, and molten salt corrosion resistance of CoNiCrAlY was investigated. The CoNiCrAlY with a 25 wt.% NiCr-Cr3C2 (NC25) cladding layer possessed the highest microhardness (348.2 HV0.3) and the smallest coefficient of friction (0.4751), exhibiting great overall mechanical properties. The generation of protective oxides Cr2O3, Al2O3, and spinel phase (Ni,Co)Cr2O4 is promoted by the addition of 25 wt.% NiCr-Cr3C2, which significantly reduces the corrosion of the cladding layer, and this effect is much more obvious at 950 °C than that at 750 °C. Furthermore, its corrosion mechanism was clarified. From the findings emerge a viable solution for the design and development of new high-temperature corrosion-resistant coatings. Full article
(This article belongs to the Special Issue Advanced Welding in Alloys and Composites)
Show Figures

Figure 1

Figure 1
<p>XRD patterns of NC5~NC30.</p>
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<p>(<b>a</b>) Mapping scan results of NC25; (<b>b</b>) microstructural morphologies of the intergranular regions; (<b>c</b>) EDS spectrum of R<sub>D</sub>.</p>
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<p>Microstructural morphologies of the cladding layers: (<b>a</b>) NC5; (<b>b</b>) NC10; (<b>c</b>) NC15; (<b>d</b>) NC20; (<b>e</b>) NC25; (<b>f</b>) NC30.</p>
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<p>The micro-hardness curves of the CoNiCrAlY and NC5~NC30 cladding layer sections.</p>
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<p>(<b>a</b>) Average COF and wear rate; (<b>b</b>) 2D images of worn surface morphology.</p>
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<p>Worn surface morphologies: (<b>a</b>) CoNiCrAlY; (<b>b</b>) NC5; (<b>c</b>) NC10; (<b>d</b>) NC15; (<b>e</b>) NC20; (<b>f</b>) NC25; (<b>g</b>) NC30.</p>
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<p>XRD patterns of CoNiCrAlY and NC5~NC30 after wear.</p>
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<p>The XRD pattern of molten salt corrosion products at 750 °C.</p>
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<p>(<b>a</b>) The surface morphology of the CoNiCrAlY cladding layer after molten salt corrosion at 750 °C; (<b>b</b>) EDS spectrum of R<sub>A</sub>.</p>
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<p>(<b>a</b>,<b>b</b>) Surface morphology of the NC25 cladding layer after molten salt corrosion at 750 °C; (<b>c</b>) EDS spectrum of R<sub>A</sub>; (<b>d</b>) EDS spectrum of R<sub>B</sub>.</p>
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<p>The cross-sectional morphology of the CoNiCrAlY cladding layer after molten salt corrosion at 750 °C and the EDS map scan results.</p>
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<p>The cross-sectional morphology of the NC25 cladding layer after molten salt corrosion at 750 °C and EDS map scan results.</p>
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<p>Corrosion weight loss curves of CoNiCrAlY and NC25 at 750 °C.</p>
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<p>The XRD patterns of molten salt corrosion products at 950 °C.</p>
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<p>(<b>a</b>) The surface morphology of the CoNiCrAlY cladding layer after molten salt corrosion at 950 °C; (<b>b</b>) EDS spectrum of R<sub>A</sub>.</p>
Full article ">Figure 16
<p>(<b>a</b>,<b>b</b>) Surface morphology of the NC25 cladding layer after molten salt corrosion at 950 °C; (<b>c</b>) EDS spectrum of R<sub>A</sub>; (<b>d</b>) EDS spectrum of R<sub>B</sub>.</p>
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<p>The cross-sectional morphology of the CoNiCrAlY cladding layer after molten salt corrosion at 950 °C and EDS map scan results.</p>
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<p>The cross-sectional morphology of the NC25 cladding layer after molten salt corrosion at 950 °C and EDS map scan results.</p>
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<p>Corrosion weight loss curves of CoNiCrAlY and NC25 at 950 °C.</p>
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<p>Schematic diagram of the NiCr<sub>2</sub>O<sub>4</sub> crystal structure.</p>
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<p>Illustration of the molten salt corrosion process.</p>
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31 pages, 7774 KiB  
Article
Monchegorsk Mafic–Ultramafic Layered PGE-Bearing Complex (2.5 Ga, Kola Region, Russia): On the Problem of Relationships between Magmatic Phases Based on the Study of Cr-Spinels
by Pavel Pripachkin, Tatiana Rundkvist, Artem Mokrushin and Aiya Bazai
Minerals 2024, 14(9), 856; https://doi.org/10.3390/min14090856 - 24 Aug 2024
Viewed by 363
Abstract
The composition of Cr-spinels from rocks of the Monchegorsk layered complex (2.5 Ga) basically corresponds to the evolutionary trend that is typical for layered mafic–ultramafic intrusions (late magmatic phases contain Cr-spinels enriched in Fe and depleted in Mg, Cr, and Al). Cr-spinels within [...] Read more.
The composition of Cr-spinels from rocks of the Monchegorsk layered complex (2.5 Ga) basically corresponds to the evolutionary trend that is typical for layered mafic–ultramafic intrusions (late magmatic phases contain Cr-spinels enriched in Fe and depleted in Mg, Cr, and Al). Cr-spinels within the Dunite Body of the Sopcha massif are almost identical to those within the Dunite Block rocks and are close to those from harzburgite of the NKT massif. Cr-spinels within the satellite bodies of the Ore Layer 330 are shown to have zonal structure, which confirms their origin from a new portion of melt, which may have been injected with several pulses. The composition of accessory Cr-spinels may indicate that the layered complex of rocks of the South Sopcha massif was formed from the most evolved portion of magmatic melt (linked with the Monchetundra intrusion), and its vein complex may be considered the one formed at the final stages of the magmatic system evolution. The composition of Cr-spinels from the Pentlandite Gorge mafic–ultramafic rocks may indicate that they are fragments of the NKT massif and not of the Monchetundra massif, as it was believed earlier. Full article
(This article belongs to the Section Mineral Deposits)
Show Figures

Figure 1

Figure 1
<p>(<b>a</b>) Scheme of the location of the main mafic–ultramafic intrusions in the central part of the Kola Region; (<b>b</b>) Geological map of the Monchegorsk layered complex. Squares with numbers are sampling sites: 1—Pentlandite Gorge; 2—South Sopcha (massif); 3—South Sopcha (Verkhniy Nude block); 4—Ore Layer 330; 5—North-East Sopcha; 6—Mine No. 5. The inset shows the position of the Monchegorsk complex on the map of the Kola Peninsula.</p>
Full article ">Figure 2
<p>(<b>a</b>) Photograph of the Pentlandite Gorge—a fragment of the Monchetundra fault expressed in the relief. (<b>b</b>) Geological map of the Pentlandite Gorge site and (<b>c</b>) section along the line A–B. White circles with signatures—sample and its number.</p>
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<p>(<b>a</b>) Geological map of the South Sopcha site. (<b>b</b>) Section along the line A–B. White circles with signatures—sample and its number.</p>
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<p>(<b>a</b>,<b>b</b>) Relationships between rocks in the South Sopcha massif. (<b>c</b>,<b>d</b>) Rocks of the vein complex of the South Sopcha site.</p>
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<p>(<b>a</b>) Outcrops of the rhythmically layered part of the Ore Layer 330. (<b>b</b>,<b>c</b>) Satellite bodies of the Ore Layer 330. (<b>d</b>) Geological map of the Sopcha massif. (<b>e</b>) Section through the Sopcha massif along the line A–B. (<b>f</b>) Geological column of the western fragment of the Ore Layer 330 (see Square 4 in <a href="#minerals-14-00856-f001" class="html-fig">Figure 1</a>b) with sampling points.</p>
Full article ">Figure 6
<p>(<b>a</b>) Position of the Dunite Body on the northeastern slope of Mount Sopcha. (<b>b</b>) Geological scheme of the Dunite Body in pyroxenites of the Sopcha massif. (<b>c</b>) Outcrops of dunites and gruss after them. (<b>d</b>) Fragment of the Dunite Body outcrop. (<b>e</b>) Serpentine vein in dunite. White circles with signatures—sample and its number.</p>
Full article ">Figure 7
<p>(<b>a</b>) Dumps of Mine No. 5 at the western foot of Mount Travyanaya. (<b>b</b>) Schematic geological section along the excavation line of Mine No. 5 [<a href="#B54-minerals-14-00856" class="html-bibr">54</a>]. Vein 4 and Vein 12 are essentially Cu-PGE-bearing sulfides.</p>
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<p>Cr-spinels from harzburgite of the Pentlandite Gorge site (Sample 9427-1700). (<b>a</b>) Cr-spinel grains in olivine and orthopyroxene. (<b>b</b>) Cr-spinel grain with thin ilmenite ingrowths (enlarged fragment of (<b>a</b>)). (<b>c</b>) Unzoned chromite grains in the center of the olivine grain and a Cr-spinel grain with a magnetite rim on the right edge of the olivine grain. (<b>d</b>) Cr-spinel grain with magnetite rim (enlarged fragment of (<b>c</b>)). BSE images.</p>
Full article ">Figure 9
<p>Cr-spinels from rocks of the South Sopcha site. (<b>a</b>) (Sample 1826/21.2) Groups of Cr-spinel grains in harzburgite of the South Sopcha massif. (<b>b</b>) (Sample Jus-8) Groups of Cr-spinel grains in harzburgite of the South Sopcha massif. (<b>c</b>) (Sample 1826/21.2) Zoned grains of Cr-spinel with magnetite rims in harzburgite of the South Sopcha massif. (<b>d</b>) (Sample 1826/144.9) Unzoned heterogeneous grain with thin ilmenite intergrowths in melanocratic norite of the South Sopcha massif; (<b>e</b>) (Sample 1a) Cr-spinel from the vein of the Verkhniy Nude block. (<b>f</b>) (Sample 2b) Cr-spinel from the vein of the Verkhniy Nude block. (<b>g</b>) (Sample 1a) Fragments of the Cr-spinel grain with intergrowths of ilmenite and ulvospinel. (<b>h</b>) (Sample 2b) Thin intergrowths of chromium magnetite (white) and ulvospinel (gray). (<b>a</b>)—polished section, (<b>b</b>–<b>h</b>)—BSE images.</p>
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<p>Chromites from the Dunite Body of the North-East Sopcha site. (<b>a</b>) Chromite grains (white) in olivine. (<b>b</b>) Early-generation chromite grains (Chr-1) in olivine. (<b>c</b>) Late-generation chromite grains (Chr-2) in the interstices between olivine grains. (<b>d</b>) Chromite crystals. (<b>a</b>–<b>c</b>)—sample M-9, (<b>d</b>)—sample M-8. BSE images.</p>
Full article ">Figure 11
<p>Cr-spinels of the Ore Layer 330 site. (<b>a</b>,<b>b</b>) (Sample S-2-2) Cr-spinels in the satellite lens of the Ore Layer 330. (<b>c</b>,<b>d</b>) (Sample Sop-Up) Cr-spinel in the upper part of the Ore Layer 330. (<b>e</b>,<b>f</b>) (Sample Sop-330) Cr-spinel in the central part of the Ore Layer 330. BSE images.</p>
Full article ">Figure 12
<p>Cr-spinels from rocks of Mine No. 5 (NKT massif). (<b>a</b>) (Sample 1-2-21) Dissemination of Cr-spinel in plagiopyroxenite. (<b>b</b>) (Sample 3-3-21) Zoned Cr-spinels in harzburgite. (<b>c</b>) (Sample 2-2-21) Heterogeneous grain of Cr-spinel in harzburgite. (<b>d</b>) (Sample 3-3-21) Zoned grains of Cr-spinel with heterogeneity of the marginal parts in harzburgite. BSE images.</p>
Full article ">Figure 13
<p>Back-scattered electron (BSE) images and element maps detailing the characteristics of Cr-spinels in the NKT massif (Mine No. 5 site). (<b>a</b>–<b>d</b>) (Sample 1-1-21) Cr-spinel grain (gray in photo (<b>a</b>)) in plagiopyroxenite with small magnetite inclusions (white in photo (<b>a</b>)) and ilmenite lattice (dark gray in photo (<b>a</b>)). (<b>e</b>–<b>h</b>) (Sample 1-1-21) Grain of Cr-spinel in plagiopyroxenite with an ilmenite lattice and a rim of high-titanium mineral phase. (<b>i</b>–<b>l</b>) (Sample 3-1-21) Zoned grain of Cr-spinel in harzburgite; the center contains small inclusions of ilmenite; and the margin is enriched in Fe.</p>
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<p>Composition of Cr-spinels of the Monchegorsk complex. (<b>a</b>) Ternary diagram Al<sup>3+</sup>-Cr<sup>3+</sup>-Fe<sup>3+</sup>. (<b>b</b>) Variation diagrams Fe<sup>2+</sup>/(Mg + Fe<sup>2+</sup>) vs. Cr/(Cr + Al). (<b>c</b>) Fe<sup>2+</sup>/(Mg + Fe<sup>2+</sup>) vs. Fe<sup>3+</sup>/(Cr + Al + Fe<sup>3+</sup>). (<b>d</b>) Fe<sup>3+</sup>/(Cr + Al + Fe<sup>3+</sup>) vs. TiO<sub>2</sub>. Red outline—layered intrusions, chromitites excluded; black outline—layered intrusions, chromitites only [<a href="#B36-minerals-14-00856" class="html-bibr">36</a>]. The red dotted arrow shows the main trend in the evolution of the MC Cr-spinels composition.</p>
Full article ">Figure 15
<p>Variation diagrams of the composition of Cr-spinels of the Monchegorsk complex: Monchetundra intrusion, Dunite Block (Sopcheozero chromite deposit), NKT, and Nude-Poaz massifs. (<b>a</b>) Mg apfu vs. Fe<sup>2+</sup> apfu. (<b>b</b>) Mg apfu vs. Fe<sup>3+</sup> apfu. (<b>c</b>) Cr<sub>2</sub>O<sub>3</sub>% vs. MgO%. (<b>d</b>) Cr<sub>2</sub>O<sub>3</sub>% vs. Al<sub>2</sub>O<sub>3</sub>%. (<b>e</b>) Al<sub>2</sub>O<sub>3</sub>% vs. MgO%. (<b>f</b>) Al apfu vs. Fe<sup>2+</sup> apfu. (<b>g</b>) Al<sub>2</sub>O<sub>3</sub>% vs. NiO%. (<b>h</b>) Al<sub>2</sub>O<sub>3</sub>% vs. ZnO%. (<b>i</b>) Al<sub>2</sub>O<sub>3</sub>% vs. MnO%. (<b>j</b>) Al<sub>2</sub>O<sub>3</sub>% vs. TiO<sub>2</sub>%. (<b>k</b>) Al<sub>2</sub>O<sub>3</sub>% vs. V<sub>2</sub>O<sub>5</sub>%.</p>
Full article ">Figure 16
<p>Chemical composition of Cr-spinels of the Monchegorsk complex. The contours of the composition fields are from <a href="#minerals-14-00856-f015" class="html-fig">Figure 15</a>. (<b>a</b>) Al<sub>2</sub>O<sub>3</sub>% vs. MgO%. (<b>b</b>) Cr<sub>2</sub>O<sub>3</sub>% vs. MgO%. (<b>c</b>) Al apfu vs. Fe<sup>2+</sup> apfu. (<b>d</b>) Al<sub>2</sub>O<sub>3</sub>% vs. ZnO%. (<b>e</b>) Al<sub>2</sub>O<sub>3</sub>% vs. TiO<sub>2</sub>%. (<b>f</b>) Al<sub>2</sub>O<sub>3</sub>% vs. V<sub>2</sub>O<sub>5</sub>%. (<b>g</b>) V<sub>2</sub>O<sub>5</sub>% vs. TiO<sub>2</sub>%. (<b>h</b>) Al<sub>2</sub>O<sub>3</sub>% vs. MnO%. (<b>i</b>) Al<sub>2</sub>O<sub>3</sub>% vs. NiO%.</p>
Full article ">
20 pages, 7710 KiB  
Article
Synthesis of MnFe2O4 Spinel on Rusted Q235 Steel Surface and Its Corrosion Resistance Properties
by Bai-Ao Feng, Xu Miao and Ting-An Zhang
Materials 2024, 17(16), 4163; https://doi.org/10.3390/ma17164163 - 22 Aug 2024
Viewed by 405
Abstract
Corrosion of steel is an issue that cannot be ignored in contemporary society. Due to large-scale corrosion, it is urgent to develop a surface treatment process that enhances the corrosion resistance of steel, allowing for application in various scenarios as needed. This study [...] Read more.
Corrosion of steel is an issue that cannot be ignored in contemporary society. Due to large-scale corrosion, it is urgent to develop a surface treatment process that enhances the corrosion resistance of steel, allowing for application in various scenarios as needed. This study aims to investigate a novel surface treatment process to extend the service life of corroded Q235 steel, reduce its sensitivity to corrosion, and enable its use in multiple environments. This study employs the sol-gel method, using manganese nitrate solutions of varying concentrations to treat the surface of Q235 steel after different electrolysis times. The optimal conditions for precursor preparation were found to be a Mn2+ concentration of 0.1 mol/L and an electrolysis time of 2 h. Electrochemical tests using NaCl solutions of different concentrations revealed a significant reduction in the corrosion current for the composite coating based on Q235 steel treated with this method in NaCl solutions with wt.% = 1, 2, 3, 4, 5. Furthermore, the resistance to corrosion was strongest in the NaCl solution with a concentration of 1 wt.% where the corrosion current decreased from 24.8 µA/cm2 to 6.79 µA/cm2. Additionally, the coating was found to be diffusion-controlled in the early stages of the corrosion process and charge transfer-controlled in the later stages. The MnFe2O4 spinel coating demonstrated the greatest enhancement in corrosion resistance in the wt.% = 1 NaCl solution. Full article
(This article belongs to the Topic Advanced Manufacturing and Surface Technology)
Show Figures

Figure 1

Figure 1
<p>Structure diagram of MnFe<sub>2</sub>O<sub>4</sub>.</p>
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<p>XRD results of samples after 60 min, 90 min, 120 min, 150 min, and 180 min of electrolysis with 0.1 mol/L Mn<sup>2+</sup> concentrations.</p>
Full article ">Figure 3
<p>FT-IR results of samples after 60 min, 90 min, 120 min, 150 min, and 180 min of electrolysis with 0.1 mol/L Mn<sup>2+</sup> concentrations. (<b>a</b>) Uncalcined precursor, (<b>b</b>) Calcined precursor.</p>
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<p>Scanning electron microscope photos of samples after (<b>a</b>) 60 min, (<b>b</b>) 90 min, (<b>c</b>) 150 min, and (<b>d</b>) 180 min of electrolysis with 0.1 mol/L Mn<sup>2+</sup> concentrations. The circles show the characteristic structures of MnFe<sub>2</sub>O<sub>4</sub> and Fe<sub>3</sub>O<sub>4</sub>.</p>
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<p>EDS diagram of samples after (<b>a</b>) 60 min, (<b>b</b>) 90 min, (<b>c</b>) 120 min, (<b>d</b>) 150 min, and (<b>e</b>) 180 min of electrolysis with 0.1 mol/L Mn<sup>2+</sup> concentrations.</p>
Full article ">Figure 5 Cont.
<p>EDS diagram of samples after (<b>a</b>) 60 min, (<b>b</b>) 90 min, (<b>c</b>) 120 min, (<b>d</b>) 150 min, and (<b>e</b>) 180 min of electrolysis with 0.1 mol/L Mn<sup>2+</sup> concentrations.</p>
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<p>Cross-sectional morphology of samples after (<b>a</b>) 60 min, (<b>b</b>) 90 min, (<b>c</b>) 150 min, and (<b>d</b>) 180 min of electrolysis with 0.1 mol/L Mn<sup>2+</sup> concentrations.</p>
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<p>XRD of samples after 120 min of electrolysis with different Mn<sup>2+</sup> concentrations: 0.02 mol/L, 0.04 mol/L, 0.06 mol/L, 0.08 mol/L, and 0.1 mol/L.</p>
Full article ">Figure 8
<p>FT-IR of samples after 120 min of electrolysis with different Mn<sup>2+</sup> concentrations: 0.02 mol/L, 0.04 mol/L, 0.06 mol/L, 0.08 mol/L, and 0.1 mol/L. (<b>a</b>) Uncalcined precursor, (<b>b</b>) Calcined precursor.</p>
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<p>Morphological patterns of samples after 120 min of electrolysis with different Mn<sup>2+</sup> concentrations: (<b>a</b>) 0.02 mol/L, (<b>b</b>) 0.04 mol/L, (<b>c</b>) 0.06 mol/L, (<b>d</b>) 0.08 mol/L, (<b>e</b>) 0.1 mol/L.</p>
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<p>Cross-sectional morphology of samples after 120 min of electrolysis with different Mn<sup>2+</sup> concentrations: (<b>a</b>) 0.08 mol/L, (<b>b</b>) 0.1 mol/L.</p>
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<p>Polarization curve of samples after 120 min of electrolysis with or without coating in NaCl solution with different mass fractions: 1%, 2%, 3%, 3.5%, 4%, and 5%. (<b>a</b>) MnFe<sub>2</sub>O<sub>4</sub> spinel coating, (<b>b</b>) Q235 steel.</p>
Full article ">Figure 12
<p>Nyquist curve of samples after 120 min of electrolysis with or without coating in NaCl solution with different mass fractions: 1%, 2%, 3%, 3.5%, 4%, and 5%. (<b>a</b>) MnFe<sub>2</sub>O<sub>4</sub> spinel coatings, (<b>b</b>) Q235 steel.</p>
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<p>Equivalent circuit diagram of fitting impedance spectrum of different substances. (<b>a</b>) MnFe<sub>2</sub>O<sub>4</sub> spinel coatings, (<b>b</b>) Q235 steel.</p>
Full article ">Figure 14
<p>Bode diagram of MnFe<sub>2</sub>O<sub>4</sub> spinel coating under different mass fractions of NaCl: 1%, 2%, 3%, 3.5%, 4%, and 5%. (<b>a</b>) Variation of impedance with frequency, (<b>b</b>) Variation of phase angle with frequency.</p>
Full article ">Figure 15
<p>The schematic diagram of the corrosion mechanism.</p>
Full article ">
12 pages, 3213 KiB  
Article
Pressure-Induced YbFe2O4-Type to Spinel Structural Change of InGaMgO4
by Takehiro Koike, Hena Das, Kengo Oka, Yoshihiro Kusano, Fernando Cubillas, Francisco Brown Bojorqez, Victor Emmanuel Alvarez-Montano, Shigekazu Ito, Kei Shigematsu, Hayato Togano, Ikuya Yamada, Hiroki Ishibashi, Yoshiki Kubota, Shigeo Mori, Noboru Kimizuka and Masaki Azuma
Solids 2024, 5(3), 422-433; https://doi.org/10.3390/solids5030028 - 19 Aug 2024
Viewed by 505
Abstract
Spinel-type InGaMgO4 with a = 8.56615(3) Å was prepared by treating layered YbFe2O4-type InGaMgO4 at 6 GPa and 1473 K. DFT calculation and Rietveld analysis of synchrotron X-ray powder diffraction data revealed the inverse spinel structure with [...] Read more.
Spinel-type InGaMgO4 with a = 8.56615(3) Å was prepared by treating layered YbFe2O4-type InGaMgO4 at 6 GPa and 1473 K. DFT calculation and Rietveld analysis of synchrotron X-ray powder diffraction data revealed the inverse spinel structure with In3+:Ga3+/Mg2+ = 0.726:0.274 in the tetrahedral site and 0.137:0.863 in the octahedral site. InGaMgO4 spinel is an insulator with an experimental band gap of 2.80 eV, and the attempt at hole doping by post-annealing in a reducing atmosphere to introduce an oxygen defect was unsuccessful. This is the first report of the bulk synthesis of AB2O4 compounds with both YbFe2O4 and spinel polymorphs. Full article
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Figure 1
<p>Crystal structures of YbFe<sub>2</sub>O<sub>4</sub> and spinel types AB<sub>2</sub>O<sub>4</sub> drawn using VESTA 3 software [<a href="#B14-solids-05-00028" class="html-bibr">14</a>].</p>
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<p>DFT-calculated and cluster-expanded formation energies of the inverse spinel phase of MgInGaO<sub>4</sub> composition as a function of In<sup>3+</sup> concentration (x). (<b>a</b>) The calculated energies of the spinel and inverse spinel phases of the end members MgGa<sub>2</sub>O<sub>4</sub> and MgIn<sub>2</sub>O<sub>4</sub> are denoted as green solid squares and red circles, respectively. The special quasi-random structures (SQS) models M<sub>SQS1</sub>, M<sub>SQS2</sub> and M<sub>SQS3</sub> correspond to <math display="inline"><semantics> <mrow> <msub> <mrow> <mfenced close="]" open="["> <mrow> <msub> <mrow> <mi>In</mi> </mrow> <mrow> <mn>0</mn> <mrow> <mo>.</mo> <mn>5</mn> </mrow> </mrow> </msub> <msub> <mrow> <mi>Ga</mi> </mrow> <mrow> <mn>0</mn> <mrow> <mo>.</mo> <mn>5</mn> </mrow> </mrow> </msub> </mrow> </mfenced> </mrow> <mrow> <msub> <mi mathvariant="normal">T</mi> <mi mathvariant="normal">d</mi> </msub> </mrow> </msub> <msub> <mrow> <mfenced close="]" open="["> <mrow> <msub> <mrow> <mi>Mg</mi> </mrow> <mrow> <mn>1</mn> <mrow> <mo>.</mo> <mn>0</mn> </mrow> </mrow> </msub> <msub> <mrow> <mi>In</mi> </mrow> <mrow> <mn>0</mn> <mrow> <mo>.</mo> <mn>5</mn> </mrow> </mrow> </msub> <msub> <mrow> <mi>Ga</mi> </mrow> <mrow> <mn>0</mn> <mrow> <mo>.</mo> <mn>5</mn> </mrow> </mrow> </msub> </mrow> </mfenced> </mrow> <mrow> <msub> <mi mathvariant="normal">O</mi> <mi mathvariant="normal">h</mi> </msub> </mrow> </msub> <msub> <mi mathvariant="normal">O</mi> <mn>4</mn> </msub> </mrow> </semantics></math>, <math display="inline"><semantics> <mrow> <msub> <mrow> <mfenced close="]" open="["> <mrow> <msub> <mrow> <mi>In</mi> </mrow> <mrow> <mn>0</mn> <mrow> <mo>.</mo> <mn>5</mn> </mrow> </mrow> </msub> <msub> <mrow> <mi>Ga</mi> </mrow> <mrow> <mn>0</mn> <mrow> <mo>.</mo> <mn>25</mn> </mrow> </mrow> </msub> <msub> <mrow> <mi>Mg</mi> </mrow> <mrow> <mn>0</mn> <mrow> <mo>.</mo> <mn>25</mn> </mrow> </mrow> </msub> </mrow> </mfenced> </mrow> <mrow> <msub> <mi mathvariant="normal">T</mi> <mi mathvariant="normal">d</mi> </msub> </mrow> </msub> <msub> <mrow> <mfenced close="]" open="["> <mrow> <msub> <mrow> <mi>Mg</mi> </mrow> <mrow> <mn>0</mn> <mrow> <mo>.</mo> <mn>75</mn> </mrow> </mrow> </msub> <msub> <mrow> <mi>In</mi> </mrow> <mrow> <mn>0</mn> <mrow> <mo>.</mo> <mn>5</mn> </mrow> </mrow> </msub> <msub> <mrow> <mi>Ga</mi> </mrow> <mrow> <mn>0</mn> <mrow> <mo>.</mo> <mn>75</mn> </mrow> </mrow> </msub> </mrow> </mfenced> </mrow> <mrow> <msub> <mi mathvariant="normal">O</mi> <mi mathvariant="normal">h</mi> </msub> </mrow> </msub> <msub> <mi mathvariant="normal">O</mi> <mn>4</mn> </msub> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <msub> <mrow> <mfenced close="]" open="["> <mrow> <msub> <mrow> <mi>In</mi> </mrow> <mrow> <mn>1</mn> <mrow> <mo>.</mo> <mn>0</mn> </mrow> </mrow> </msub> </mrow> </mfenced> </mrow> <mrow> <msub> <mi mathvariant="normal">T</mi> <mi mathvariant="normal">d</mi> </msub> </mrow> </msub> <msub> <mrow> <mfenced close="]" open="["> <mrow> <msub> <mrow> <mi>Mg</mi> </mrow> <mrow> <mn>1</mn> <mrow> <mo>.</mo> <mn>0</mn> </mrow> </mrow> </msub> <msub> <mrow> <mi>Ga</mi> </mrow> <mrow> <mn>1</mn> <mrow> <mo>.</mo> <mn>0</mn> </mrow> </mrow> </msub> </mrow> </mfenced> </mrow> <mrow> <msub> <mi mathvariant="normal">O</mi> <mi mathvariant="normal">h</mi> </msub> </mrow> </msub> <msub> <mi mathvariant="normal">O</mi> <mn>4</mn> </msub> </mrow> </semantics></math> configurations, where <math display="inline"><semantics> <mrow> <msub> <mi mathvariant="normal">T</mi> <mi mathvariant="normal">d</mi> </msub> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <msub> <mi mathvariant="normal">O</mi> <mi mathvariant="normal">h</mi> </msub> </mrow> </semantics></math> denote tetrahedral (multiplicity = 8) and octahedra (multiplicity = 16) sites, respectively. (<b>b</b>) Estimated values of effective cluster interactions (ECI) for two sites (top panel), three sites (middle panel) and four sites (bottom panel) clusters.</p>
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<p>(<b>a</b>) Calculated band structure (left panel) and optical absorption (right panel) for the layered phase of InGaMnO<sub>4</sub>, corresponding to the lowest-energy cation-ordered structure using hybrid potential. (<b>b</b>) Calculated band structure (left panel) and optical absorption (right panel) for the inverse spinel phase of InGaMnO<sub>4</sub>, corresponding to the lowest-energy cation-ordered structure using hybrid potential. The gray band in (<b>b</b>) represents the visible spectrum of light.</p>
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<p>Calculated formation energies (<math display="inline"><semantics> <mrow> <mo>∆</mo> <msup> <mi>E</mi> <mi mathvariant="bold-italic">f</mi> </msup> </mrow> </semantics></math>) of charged oxygen vacancy <math display="inline"><semantics> <mrow> <msubsup> <mi>V</mi> <mi>O</mi> <mrow> <mo>·</mo> <mo>·</mo> </mrow> </msubsup> </mrow> </semantics></math> as a function of oxygen partial pressure and temperature for the inverse spinel (<b>a</b>) and layered (<b>b</b>) phases of InGaMgO<sub>4</sub>. The <math display="inline"><semantics> <mrow> <msub> <mi>E</mi> <mi>f</mi> </msub> </mrow> </semantics></math> was set at the valence band maximum. (<b>c</b>) Calculated energy band gap (E<sub>g</sub>) of the inverse spinel phase of InGaMgO<sub>4-<span class="html-italic">x</span></sub> as a function of oxygen defect concentration <span class="html-italic">x</span> at the level of HSE06. (<b>d</b>) Estimated band gap values corresponding to the crystals with charged cation and oxygen defects with 0.125 concentration at the level of HSE06. The dashed line denotes the band gap value for the perfect crystal.</p>
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<p>Observed (red points), calculated (green line) and difference (blue line) patterns of YbFe<sub>2</sub>O<sub>4</sub>-type InGaMgO<sub>4</sub> from the result of the Rietveld analysis of the SXRD data at room temperature (λ = 0.500606 Å). The green tick marks indicate the positions of Bragg reflections of YbFe<sub>2</sub>O<sub>4</sub>-type InGaMgO<sub>4</sub>, In<sub>2</sub>O<sub>3</sub> and MgGa<sub>2</sub>O<sub>4</sub> phases from top to bottom. The reliability factors of the refinement were <span class="html-italic">R</span><sub>WP</sub> = 9.62% and <span class="html-italic">R</span><sub>I</sub> = 1.67%. The weight fractions of the impurity of In<sub>2</sub>O<sub>3</sub> and MgGa<sub>2</sub>O<sub>4</sub> phases were estimated to be 0.3 and 1.7 wt%, respectively. The crystal structure of YbFe<sub>2</sub>O<sub>4</sub>-type InGaMgO<sub>4</sub> was visualized using VESTA 3 software [<a href="#B14-solids-05-00028" class="html-bibr">14</a>].</p>
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<p>TEM image, ED and NBD patterns of YbFe<sub>2</sub>O<sub>4</sub>-type InGaMgO<sub>4</sub>. a and b are the ED images of the corresponding area in the main panel. c–f are the NBD patterns of the corresponding area in the main panel.</p>
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<p>Observed (red points), calculated (green line) and difference (blue line) patterns of spinel InGaMgO<sub>4</sub> from the result of the Rietveld analysis of the SXRD data at room temperature (λ = 0.500606 Å). The tick marks correspond to the positions of Bragg reflections of the InGaMgO<sub>4</sub> spinel and In<sub>2</sub>O<sub>3</sub> phases from top to bottom. The reliability factors of the refinement were <span class="html-italic">R</span><sub>WP</sub> = 7.960% and <span class="html-italic">R</span><sub>I</sub> = 2.648%. The weight fraction of the impurity of In<sub>2</sub>O<sub>3</sub> was estimated to be 3.3 wt%. The crystal structure of the InGaMgO<sub>4</sub> spinel phase was visualized using VESTA 3 software [<a href="#B14-solids-05-00028" class="html-bibr">14</a>].</p>
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<p>(<b>a</b>) The diffuse reflectance spectrum and (<b>b</b>) Tauc plots of spinel phase.</p>
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16 pages, 2734 KiB  
Article
Evolution of the Corrosion Products around MnS Embedded in AISI 304 Stainless Steel in NaCl Solution
by Dan Li, Hongliang Hao, Zhichao Wang and Edwin Ernest Nyakilla
Materials 2024, 17(16), 4050; https://doi.org/10.3390/ma17164050 - 15 Aug 2024
Viewed by 445
Abstract
The characterization and evolution of corrosion products deposited on/around MnSs, a typical kind of inclusive particle embedded in AISI 304 stainless steel, was analyzed using a quasi-in-situ method in a 3.5 wt.% NaCl solution. On/around the MnS inclusion, a corrosion product layer with [...] Read more.
The characterization and evolution of corrosion products deposited on/around MnSs, a typical kind of inclusive particle embedded in AISI 304 stainless steel, was analyzed using a quasi-in-situ method in a 3.5 wt.% NaCl solution. On/around the MnS inclusion, a corrosion product layer with spinel Fe3−xCrxO4 as the main component was formed, with a thickness of several hundred nanometers. Below the layer, there was a cavity layer in which part of the MnS remained, forming secondary pitting along the MnS/matrix boundary. The mechanism of corrosion product deposition and evolution accompanied by MnS dissolution, as well as the characteristics of the corrosion products, are discussed. Full article
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<p>OM morphology of rod-shaped MnS inclusions formed in the re-sulfurized stainless steel.</p>
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<p>SEM morphology and EDS mapping results of (<b>a</b>) rod-shaped inclusions of different sizes in a wide field of view and (<b>b</b>) an individual inclusion.</p>
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<p>SEM morphologies of (<b>a</b>) MnS-1, (<b>b</b>) MnS-2, and (<b>c</b>) MnS-3 after immersion in 3.5 wt.% NaCl solution for 0 h, 20 h, 40 h, and 60 h, respectively.</p>
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<p>(<b>a</b>) Overall SEM morphology of the corrosion products deposited around MnS-3 after 20 h of immersion. (<b>b</b>) Enlarged image of the marked area in <a href="#materials-17-04050-f004" class="html-fig">Figure 4</a>a, and the corresponding (<b>c</b>) EDS mapping of the corrosion products.</p>
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<p>Raman spectra of MnS after different immersion times. (<b>a</b>) The peak at 279 cm<sup>−1</sup> is MnS, whose intensity decreases with time; the peak at 636 cm<sup>−1</sup> represents Fe<sub>3−x</sub>Cr<sub>x</sub>O<sub>4</sub>; the peak at 497 cm<sup>−1</sup> appearing after 40 h of immersion belongs to FeOOH. In addition, the weak peak (424 cm<sup>−1</sup>) appearing at 20 h and 40 h may be Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>3</sub>. (<b>b</b>) An extremely weak peak at 352 cm<sup>−1</sup> appearing at 60 h may be Cr<sub>2</sub>O<sub>3</sub>.</p>
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<p>AFM topographies and correlation height profiles (white lines) of MnS-3 inclusion after immersion for different times: (<b>a</b>) 0 h, (<b>b</b>) 20 h, (<b>c</b>) 40 h, and (<b>d</b>) 60 h.</p>
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<p>AFM results for MnS-1 and MnS-2. (<b>a</b>) Topography and (<b>b</b>) surface Volta potential of MnS-1 at 0 h; (<b>c</b>) Topography and (<b>d</b>) surface Volta potential of MnS-1 at 20 h; (<b>e</b>) Topography and (<b>f</b>) surface Volta potential of MnS-2 at 0 h; (<b>g</b>) Topography and (<b>h</b>) surface Volta potential of MnS-2 at 20 h.</p>
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<p>FIB-SEM images of MnS-3 after immersion for 60 h. (<b>a</b>) MnS-3 was cut along the cut line. (<b>b</b>) Cross-sectional morphology of MnS-3. (<b>c</b>) Magnified image of the area surrounded by black dashed lines in figure (<b>a</b>).</p>
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<p>SEM morphology of (<b>a</b>) MnS-1 and (<b>b</b>) MnS-2 after removal of corrosion products formed after 60 h of immersion. Raman spectra of (<b>a</b>) MnS-1 and (<b>b</b>) MnS-2 collected in the area enclosed by the red circle. (<b>c</b>,<b>d</b>) Raman spectra taken at the middle of the pit formed by MnS-1 and MnS-2.</p>
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<p>Brief schematic diagram of morphological changes on/around an MnS. (<b>a</b>) The original morphology of an MnS. (<b>b</b>) MnS dissolves from its boundary areas and releases S. (<b>c</b>) The peripheral active matrix is exposed and begins to dissolve, forming trenches along the MnS/matrix boundary. (<b>d</b>) As the corrosion product layer is deposited and covers the inclusion and its surrounding matrix, a cavity layer is formed under the layer. (<b>e</b>) The corrosion product layer slowly thickens with time, and in addition to the formation of FeOOH at the pit mouth beneath the layer, secondary pitting with a tendency to expand towards the inner matrix also occurs.</p>
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<p>A brief schematic diagram of the trench along the MnS/matrix boundary.</p>
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13 pages, 4635 KiB  
Article
Recycling and Reuse of Mn-Based Spinel Electrode from Spent Lithium-Ion Batteries
by Arjun K. Thapa, Abhinav C. Nouduri, Mohammed Mohiuddin, Hari Prasad Reddy Kannapu, Lihui Bai, Hui Wang and Mahendra K. Sunkara
Energies 2024, 17(16), 3996; https://doi.org/10.3390/en17163996 - 12 Aug 2024
Viewed by 662
Abstract
In this paper, we introduce an environmentally friendly approach to recycle used batteries and recover highly valuable manganese-based cathode materials. This study demonstrates the feasibility of fast plasma pyrolysis to recover LiMn2O4 electrode materials (e.g., lithium manganese oxide, LMO) and [...] Read more.
In this paper, we introduce an environmentally friendly approach to recycle used batteries and recover highly valuable manganese-based cathode materials. This study demonstrates the feasibility of fast plasma pyrolysis to recover LiMn2O4 electrode materials (e.g., lithium manganese oxide, LMO) and demonstrate their reuse in newly assembled Li-ion cells. The electrochemical performance of as-recycled cathodes shows an initial discharge capacity of 72 mAh/g and is stable for 100 cycles at 0.1 C. After adding 20 mole % of excess LiOH, the recycled LMO after relithiation at 660 °C can deliver an initial discharge capacity of 96 mAh/g and retain a decent discharge capacity of 88 mAh/g after 50 cycles at a 0.2 C rate. Without relithiation, the as-recycled LMO cathode after heating at 1000 °C delivers the best electrochemical cycling performance, including an initial discharge capacity of 94 mAh/g and 50th cycle capacity of 91 mAh/g at a 0.2 C rate. This study highlights a feasible approach for recycling electrode materials in spent LIBs. Recycling of lithium-ion batteries and especially electrode materials is crucial for the sustained growth of the lithium-ion battery industry and reduced environmental issues. Full article
(This article belongs to the Section D: Energy Storage and Application)
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<p>Images of the as-recycled (<b>a</b>) LiMn<sub>2</sub>O<sub>4</sub> cathode and (<b>b</b>) anode (carbon) powders (after washing with ethanol and sieving).</p>
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<p>X-ray diffraction patterns of commercial LiMn<sub>2</sub>O<sub>4</sub> (bottom), as-recycled LiMn<sub>2</sub>O<sub>4</sub> (middle), and LiOH-added LiMn<sub>2</sub>O<sub>4</sub> (top).</p>
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<p>(<b>a</b>,<b>b</b>) SEM images of as-recycled LiMn<sub>2</sub>O<sub>4</sub> powder under different magnifications.</p>
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<p>(<b>a</b>) Charge–discharge curves and (<b>b</b>) cycle performance of as-recycled LiMn<sub>2</sub>O<sub>4</sub> cathode from plasma treatment. The cells were cycled at 0.1 C rate with liquid electrolyte 1M LiPF<sub>6</sub>-EC:DMC (1:2) within voltage window of 3.0–4.3 V.</p>
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<p>(<b>a</b>) The charge–discharge curves and (<b>b</b>) cycle performance of new LIBs with five different cathode materials: as-recycled LiMn<sub>2</sub>O<sub>4</sub> cathode; a mixture of 80 wt% as-recycled + 20 wt% commercial LiMn<sub>2</sub>O<sub>4</sub> cathode; a mixture of 40 wt% as-recycled + 60 wt% commercial LiMn<sub>2</sub>O<sub>4</sub> cathode; commercial LiMn<sub>2</sub>O<sub>4</sub>, and recycled LiMn<sub>2</sub>O<sub>4</sub> after adding 0.2M LiOH for relithiation. The cells were cycled at a 0.2 C rate with the liquid electrolyte 1M LiPF<sub>6</sub>-EC:DMC (1:2)-2 wt% FEC within a voltage window of 3.0–4.3 V.</p>
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<p>Cyclic voltammetry curves of as-recycled LiMn<sub>2</sub>O<sub>4</sub>, recycled LiMn<sub>2</sub>O<sub>4</sub> after adding LiOH, and commercial LiMn<sub>2</sub>O<sub>4</sub> cathode electrodes scan at speed of 0.1 mV/s.</p>
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<p>(<b>a</b>) The charge–discharge curves and (<b>b</b>) cycle performance of the regenerated LiMn<sub>2</sub>O<sub>4</sub> cathode at 800, 900, and 1000 °C-10 h. The cells were cycled at the current of a 0.2 C rate within a voltage of 2.5–4.7 V.</p>
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<p>Cyclic voltammetry results of regenerated LiMn<sub>2</sub>O<sub>4</sub> cathode electrodes at (<b>a</b>) 800 °C, (<b>b</b>) 900 °C, and (<b>c</b>) 1000 °C with scanning speed of 0.1 mV/s.</p>
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30 pages, 9980 KiB  
Article
Enhanced Removal of Cd(II) Ions from Aqueous Media via Adsorption on Facilely Synthesized Copper Ferrite Nanoparticles
by Nada S. Al-Kadhi and Maram T. Basha
Molecules 2024, 29(15), 3711; https://doi.org/10.3390/molecules29153711 - 5 Aug 2024
Viewed by 770
Abstract
In this study, magnetic copper ferrite (CuFe2O4) nanoparticles were synthesized via the Pechini sol-gel method and evaluated for the removal of Cd(II) ions from aqueous solutions. PF600 and PF800 refer to the samples that were synthesized at 600 °C [...] Read more.
In this study, magnetic copper ferrite (CuFe2O4) nanoparticles were synthesized via the Pechini sol-gel method and evaluated for the removal of Cd(II) ions from aqueous solutions. PF600 and PF800 refer to the samples that were synthesized at 600 °C and 800 °C, respectively. Comprehensive characterization using FTIR, XRD, FE-SEM, HR-TEM, and EDX confirmed the successful formation of CuFe2O4 spinel structures, with crystallite sizes of 22.64 nm (PF600) and 30.13 nm (PF800). FE-SEM analysis revealed particle diameters of 154.98 nm (PF600) and 230.05 nm (PF800), exhibiting spherical and irregular shapes. HR-TEM analysis further confirmed the presence of aggregated nanoparticles with average diameters of 52.26 nm (PF600) and 98.32 nm (PF800). The PF600 and PF800 nanoparticles exhibited exceptional adsorption capacities of 377.36 mg/g and 322.58 mg/g, respectively, significantly outperforming many materials reported in the literature. Adsorption followed the Langmuir isotherm model and pseudo-second-order kinetics, indicating monolayer adsorption and strong physisorption. The process was spontaneous, exothermic, and predominantly physical. Reusability tests demonstrated high adsorption efficiency across multiple cycles when desorbed with a 0.5 M ethylenediaminetetraacetic acid (EDTA) solution, emphasizing the practical applicability of these nanoparticles. The inherent magnetic properties of CuFe2O4 facilitated easy separation from the aqueous medium using a magnet, enabling efficient and cost-effective recovery of the adsorbent. These findings highlight the potential of CuFe2O4 nanoparticles, particularly PF600, for the effective and sustainable removal of Cd(II) ions from water. Full article
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<p>XRD analysis of the PF600 (<b>A</b>) and PF800 (<b>B</b>) products. Standard JCPDS No. 77-0010 (<b>C</b>).</p>
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<p>EDX analysis of the PF600 (<b>A</b>) and PF800 (<b>B</b>) products.</p>
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<p>FTIR analysis of the PF600 (<b>A</b>) and PF800 (<b>B</b>) products.</p>
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<p>FE-SEM analysis of the PF600 (<b>A</b>) and PF800 (<b>B</b>) samples.</p>
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<p>FE-SEM histograms of the PF600 (<b>A</b>) and PF800 (<b>B</b>) samples.</p>
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<p>HR-TEM analysis of the PF600 (<b>A</b>) and PF800 (<b>B</b>) products.</p>
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<p>The adsorption percentage of cadmium ions on the PF600 and PF800 products throughout a range of pH values (<b>A</b>). The point of zero charge (pH<sub>PZC</sub>) of the PF600 and PF800 products (<b>B</b>).</p>
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<p>FE-SEM image of the PF600 sample after Cd(II) adsorption at magnifications of 15,000× (<b>A</b>) and 3000× (<b>B</b>).</p>
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<p>FTIR spectrum of the PF600 sample after Cd(II) adsorption.</p>
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<p>Impact of contact time on the adsorption percentage of cadmium ions by the PF800 and PF600 products.</p>
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<p>Linear kinetic modeling of Cd(II) ions adsorption onto the PF800 and PF600 products by the pseudo-first-order (<b>A</b>) as well as the pseudo-second-order (<b>B</b>) kinetic plots.</p>
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<p>Non-linear kinetic modeling of Cd(II) ion adsorption onto the PF800 and PF600 products by the pseudo-first-order (<b>A</b>) as well as the pseudo-second-order (<b>B</b>) kinetic plots.</p>
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<p>Impact of temperature on the adsorption percentage of cadmium ions by the PF800 and PF600 products (<b>A</b>). The plot of ln L<sub>d</sub> versus 1/T (<b>B</b>).</p>
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<p>Impact of adsorbent dosage on the adsorption percentage of cadmium ions by the PF800 and PF600 products.</p>
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<p>Impact of initial Cd(II) concentration on the adsorption percentage of Cd(II) ions by the PF800 and PF600 samples.</p>
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<p>Linear equilibrium modeling of Cd(II) ion adsorption onto the PF800 and PF600 products by the Langmuir (<b>A</b>) and the Freundlich (<b>B</b>) equilibrium plots.</p>
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<p>Non-linear equilibrium modeling of Cd(II) ion adsorption onto the PF800 and PF600 products by the Langmuir (<b>A</b>) as well as the Freundlich (B) equilibrium plots.</p>
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<p>Impact of reusability of the PF800 and PF800 products for the sorption of cadmium ions.</p>
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<p>Production of copper ferrite nanoparticles through the Pechini sol-gel process.</p>
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<p>Removal mechanism of cadmium ions by the synthesized copper ferrite nanoparticles.</p>
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<p>Practical steps for producing copper ferrite (CuFe<sub>2</sub>O<sub>4</sub>) nanoparticles using the Pechini sol-gel method.</p>
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<p>Experimental influences for studying the adsorption of Cd(II) ions by the PF600 and PF800 products.</p>
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<p>Assessing the regeneration and reusability of adsorbents in the removal of Cd(II) ions under optimal conditions.</p>
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11 pages, 1648 KiB  
Article
Synthesis of New Complex Ferrite Li0.5MnFe1.5O4: Chemical–Physical and Electrophysical Research
by Mukhametkali Mataev, Altynai Madiyarova, Gennady Patrin, Moldir Abdraimova, Marzhan Nurbekova and Zhadyra Durmenbayeva
Materials 2024, 17(15), 3754; https://doi.org/10.3390/ma17153754 - 30 Jul 2024
Viewed by 1835
Abstract
In this article, the sol–gel method was used as a synthesis method, which shows the physicochemical nature of the synthesis of a new complex material, ferrite Li0.5MnFe1.5O4. The structure and composition of the synthesized ferrite were determined [...] Read more.
In this article, the sol–gel method was used as a synthesis method, which shows the physicochemical nature of the synthesis of a new complex material, ferrite Li0.5MnFe1.5O4. The structure and composition of the synthesized ferrite were determined by X-ray phase analysis. According to analysis indicators, it was found that our compound is a single-phase, spinel-structured, and syngony-cubic type of compound. The microstructure of the compound and the quantitative composition of the elements contained within it were analyzed under a scanning electron microscope (SEM). Under a scanning electron microscope, microsystems were taken from different parts of Li0.5MnFe1.5O4-type crystallite; the elemental composition of crystals was analyzed; and the general type of surface layer of complex ferrite was shown. As a result, given the fact that the compound consists of a single phase, the clarity of its construction was determined by the topography and chemical composition of the compound. As a result, it was found that the newly synthesized complex ferrites correspond to the formula Li0.5MnFe1.5O4. The particles of the formed compounds have a large size (between 50.0 μm or 20.0 μm and 10.0 μm). Electrophysical measurements were carried out on an LCR-800 unit at intervals of 293–483 K and at frequencies of 1.5 and 10 kHz. An increase in frequency to 10 kHz led to a decrease in the value ε in the range of the studied temperature (293–483 K). Full article
(This article belongs to the Section Materials Chemistry)
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<p>X-ray diffractogram of the complex ferrite Li<sub>0.5</sub>MnFe<sub>1.5</sub>O<sub>4</sub>. Insert: phase ratio diagram.</p>
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<p>Image of the new mixed complex ferrite Li<sub>0.5</sub>MnFe<sub>1.5</sub>O<sub>4</sub> measured with three different micrometer accuracies: (<b>a</b>) 10 μm; (<b>b</b>) 20 μm; (<b>c</b>) 50 μm.</p>
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<p>Spectrum samples of the Li<sub>0.5</sub>MnFe<sub>1.5</sub>O<sub>4</sub> compound. The results of the element analysis are built-in.</p>
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<p>Dependence of dielectric constant (<b>a</b>) and electrical resistance (<b>b</b>) on temperature and frequency equal to 1 kHz.</p>
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39 pages, 3950 KiB  
Article
Expanded Insights into Martian Mineralogy: Updated Analysis of Gale Crater’s Mineral Composition via CheMin Crystal Chemical Investigations
by Shaunna M. Morrison, David F. Blake, Thomas F. Bristow, Nicholas Castle, Steve J. Chipera, Patricia I. Craig, Robert T. Downs, Ahmed Eleish, Robert M. Hazen, Johannes M. Meusburger, Douglas W. Ming, Richard V. Morris, Aditi Pandey, Anirudh Prabhu, Elizabeth B. Rampe, Philippe C. Sarrazin, Sarah L. Simpson, Michael T. Thorpe, Allan H. Treiman, Valerie Tu, Benjamin M. Tutolo, David T. Vaniman, Ashwin R. Vasavada and Albert S. Yenadd Show full author list remove Hide full author list
Minerals 2024, 14(8), 773; https://doi.org/10.3390/min14080773 - 29 Jul 2024
Cited by 2 | Viewed by 858
Abstract
This study presents mineral composition estimates of rock and sediment samples analyzed with the CheMin X-ray diffraction instrument on board the NASA Mars Science Laboratory rover, Curiosity, in Gale crater, Mars. Mineral composition is estimated using crystal-chemically derived algorithms applied to X-ray [...] Read more.
This study presents mineral composition estimates of rock and sediment samples analyzed with the CheMin X-ray diffraction instrument on board the NASA Mars Science Laboratory rover, Curiosity, in Gale crater, Mars. Mineral composition is estimated using crystal-chemically derived algorithms applied to X-ray diffraction data, specifically unit-cell parameters. The mineral groups characterized include those found in major abundance by the CheMin instrument (i.e., feldspar, olivine, pyroxene, and spinel oxide). In addition to estimating the composition of the major mineral phases observed in Gale crater, we place their compositions in a stratigraphic context and provide a comparison to that of martian meteorites. This work provides expanded insights into the mineralogy and chemistry of the martian surface. Full article
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<p>Plagioclase composition (as Ca apfu) of the fluviolacustrine and cemented eolian samples analyzed by the CheMin instrument along the Gale crater stratigraphic section. Error bars represent uncertainty to 1σ. Plagioclase abundance as wt. % of the crystalline sample fraction is displayed as a gray line. The WJ sample was excluded due to its large uncertainty.</p>
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<p>Frequency of occurrence of plagioclase as a function of composition [Ca/(Ca+Na)] in martian meteorites (brown) and Gale crater samples analyzed by CheMin (transparent tan overlay).</p>
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<p>Alkali feldspar unit-cell parameters plotted on the alkali feldspar quadrilateral (<span class="html-italic">b</span> unit-cell parameter versus <span class="html-italic">c</span> unit-cell parameter, after Morrison et al. (2018) [<a href="#B8-minerals-14-00773" class="html-bibr">8</a>,<a href="#B9-minerals-14-00773" class="html-bibr">9</a>]. CheMin samples shown in blue, with error bars corresponding to 1σ uncertainty.</p>
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<p>Frequency of occurrence of alkali feldspar as a function of composition [Na/(Na+K)] in martian meteorites (brown) and Gale crater samples analyzed by CheMin (transparent tan overlay).</p>
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<p>Feldspar composition as a function of Or (% KAlSi<sub>3</sub>O<sub>8</sub>), Ab (% NaAlSi<sub>3</sub>O<sub>8</sub>), and An (% CaAl<sub>2</sub>Si<sub>2</sub>O<sub>8</sub>) in martian meteorites and Gale crater samples analyzed by CheMin. Gale crater sample error bars are at 1σ uncertainty.</p>
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<p>Frequency of occurrence of olivine as a function of composition [Mg/(Mg + Fe)] in martian meteorites (brown) and Gale crater samples analyzed by CheMin (transparent tan overlay).</p>
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<p>Pyroxene sample composition as a function of Ca (%), Mg (%), and Fe (%) in martian meteorites and Gale crater samples analyzed by CheMin. Gale crater sample error bars are at 1σ uncertainty.</p>
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<p>Select spinel oxide phases (<span class="html-italic">M</span><sub>3</sub>O<sub>4</sub>) as a function of Fe content and <span class="html-italic">a</span> unit-cell parameter. The blue region represents the range of Gale crater spinel oxide <span class="html-italic">a</span> unit-cell parameters. Purple circles represent the MgAl<sub>2</sub>O<sub>4</sub>-FeAl<sub>2</sub>O<sub>4</sub> solid solution series, orange circles represent FeAl<sub>2</sub>O<sub>4</sub>-Fe<sub>3</sub>O<sub>4</sub>, light blue circles represent Fe<sub>2.7</sub><b>☐</b><sub>0.03</sub>-Fe<sub>3</sub>O<sub>4</sub>, dark blue circles represent NiFe<sub>2</sub>O<sub>4</sub>-Fe<sub>3</sub>O<sub>4</sub>, grey circles represent MgFe<sub>2</sub>O<sub>4</sub>-Fe<sub>3</sub>O<sub>4</sub>, cyan circles represent FeCr<sub>2</sub>O<sub>4</sub>-MgCr<sub>2</sub>O<sub>4</sub>, dark green circles represent FeV<sub>2</sub>O<sub>4</sub>-Fe<sub>3</sub>O<sub>4</sub>, light purple circles represent ZnFe<sub>2</sub>O<sub>4</sub>-Fe<sub>3</sub>O<sub>4</sub>, light green circles represent TiFe<sub>2</sub>O<sub>4</sub>-Fe<sub>3</sub>O<sub>4</sub>, red circles represent TiFe<sub>2</sub>O<sub>4</sub>-TiMg<sub>2</sub>O<sub>4</sub>, and pink circles represent TiFe<sub>2</sub>O<sub>4</sub>-TiMn<sub>2</sub>O<sub>4</sub> solid solution series.</p>
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<p>Violin plot of martian meteorite spinel oxide elemental concentrations (apfu) distributions. Each violin represents the distribution of major elements (Fe, Mg, Al, Cr, and Ti) across the 531 sampled meteorites. The width of each violin indicates the density of data points.</p>
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<p>Cubic spinel oxide composition as magnetite–maghemite (Fe apfu solid solution with site vacancy) of the fluviolacustrine and cemented eolian samples analyzed by the CheMin instrument along the Gale crater stratigraphic section. Error bars represent uncertainty to 1σ. Spinel oxide abundance as wt. % of the crystalline sample fraction is displayed as a gray line.</p>
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19 pages, 7801 KiB  
Article
Gemological and Chemical Characterization of Gem-Grade Peridot from Yiqisong, Jilin Province
by Jina Li, Yi Zhao and Bo Xu
Crystals 2024, 14(8), 689; https://doi.org/10.3390/cryst14080689 - 27 Jul 2024
Viewed by 600
Abstract
Peridot has a long history and is deeply loved by people for its unique olive-green color. The Yiqisong peridot deposit in Jilin Province is a newly discovered peridot deposit that still deserves systematic research. In this study, gemological and chemical analyses of thirty-three [...] Read more.
Peridot has a long history and is deeply loved by people for its unique olive-green color. The Yiqisong peridot deposit in Jilin Province is a newly discovered peridot deposit that still deserves systematic research. In this study, gemological and chemical analyses of thirty-three Yiqisong peridot samples were carried out to investigate the gemological characteristics, as well as the mantle properties and formation conditions of the Yiqisong. In addition, we identified gemological differences in peridot between Yiqisong, Tanzania, and Arizona. The Yiqisong peridot samples have typical peridot gemological characteristics. The UV–visible spectrum indicated that Fe is the chromogenic element. The infrared spectra and Raman spectra of different samples are consistent, which indicates that the Yiqisong peridot belongs to forsterite. The contents of Ni and V in Yiqisong peridot are generally low, distinguishing it from peridot found in Tanzania and Arizona. The major and trace elements of samples show that the Yiqisong peridot is derived from the spinel lherzolite xenoliths with the P–T formation conditions of 813–1087 °C and 21–22 kbar. The Yisqisong peridot samples have relatively high Fo values (up to 91.6), supporting their origin from a moderate refractory lithosphere mantle. Therefore, this study provides gemological, mineralogical, and chemical evidence that fills the research gap in peridot deposit studies and lays the foundation for follow-up investigations of gem-grade peridot deposits. Full article
(This article belongs to the Special Issue The Progress of In-Situ Study of Mineralogy and Gemmology)
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<p>(<b>a</b>) Schematic diagram showing the main tectonic subdivisions of central and eastern Asia (modified from Zhang [<a href="#B18-crystals-14-00689" class="html-bibr">18</a>]); (<b>b</b>) sketch geological map of northeast (NE) China, showing the distribution of the Cenozoic volcanic rocks and peridotite xenoliths in the area (modified from Zhang [<a href="#B18-crystals-14-00689" class="html-bibr">18</a>]); (<b>c</b>) gem-grade peridot deposit map in Yiqisong, Dunhua of Jilin Province (modified from Xu [<a href="#B16-crystals-14-00689" class="html-bibr">16</a>]).</p>
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<p>(<b>A</b>) The thirty-three Yiqisong peridot rough samples collected and examined for this study; (<b>B</b>–<b>E</b>) representative samples for magnified photography.</p>
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<p>Internal features of Yiqisong peridot: (<b>a</b>) conchoidal fractures on the peridot surface (YQS–30); (<b>b</b>) rhombohedral growth etch pits on the crystal faces (YQS–14); (<b>c</b>) granular inclusions in YQS–14; (<b>d</b>) YQS–30 internal negative crystal; (<b>e</b>) YQS–30 internal cleavages with iridescence effect; (<b>f</b>,<b>g</b>) YQS–30 and YQS–14 internal “Lily pad” inclusions; (<b>h</b>) YQS–30 internal polyphase inclusion.</p>
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<p>The diopside (<b>a</b>) and spinel (<b>b</b>,<b>c</b>) inclusions in Yiqisong peridot. Their Raman spectra were used to prove the mineral species.</p>
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<p>The representative UV–vis–NIR spectra of Yiqisong peridots. They are mainly characterized by Fe<sup>2+</sup> absorption features.</p>
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<p>The representative FTIR spectrum was obtained from Yiqisong peridot. The marked absorption bands are related to the symmetrical stretching vibration of the Si–O–Si group (1100~800 cm<sup>−1</sup>), the bending vibration of the Si–O group (650~450 cm<sup>−1</sup>), and internal vibrations and lattice vibrations (450~400 cm<sup>−1</sup>).</p>
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<p>Raman spectrum of Yiqisong peridots is mainly characterized by the vibration of Si–O (824 and 856 cm<sup>−1</sup>).</p>
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<p>Two-dimensional scatter plots of trace element contents in peridot from three geographic origins: (<b>A</b>) 2D plots of Co-Cr; (<b>B</b>) 2D plots of Mn-Co; (<b>C</b>) 2D plots of Ni-Sc; (<b>D</b>) 2D plots of Sc-Cr; (<b>E</b>) 2D plots of Sc-V; (<b>F</b>) 2D plots of V-Mn.</p>
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<p>Fo value distribution of peridot in Yiqisong, Jiaohe [<a href="#B52-crystals-14-00689" class="html-bibr">52</a>], Shanwang [<a href="#B53-crystals-14-00689" class="html-bibr">53</a>], and Hebi [<a href="#B54-crystals-14-00689" class="html-bibr">54</a>] peridotite xenoliths.</p>
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<p>Discrimination diagrams to identify the parent-rock lithologies based on trace elements. Green triangles for Yiqisong peridots, purple area for peridots from spinel peridotites, and yellow area for peridots from garnet peridotites. The data of spinel peridotites and garnet peridotites are from De Hoog [<a href="#B41-crystals-14-00689" class="html-bibr">41</a>].</p>
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<p>The equilibrium structure between clinopyroxenes and orthopyroxenes.</p>
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<p>P–T diagram of Yiqisong peridotites. The data of Dashihe peridotites are from Han [<a href="#B60-crystals-14-00689" class="html-bibr">60</a>].</p>
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15 pages, 625 KiB  
Article
Designing Strain-Less Electrode Materials: Computational Analysis of Volume Variations in Li-Ion and Na-Ion Batteries
by Maxime Maréchal, Romain Berthelot, Patrick Rozier and Matthieu Saubanère
Batteries 2024, 10(8), 262; https://doi.org/10.3390/batteries10080262 - 25 Jul 2024
Viewed by 567
Abstract
Mechanical degradation in electrode materials during successive electrochemical cycling is critical for battery lifetime and aging properties. A common strategy to mitigate electrode mechanical degradation is to suppress the volume variation induced by Li/Na intercalation/deintercalation, thereby designing strain-less electrodes. In this study, we [...] Read more.
Mechanical degradation in electrode materials during successive electrochemical cycling is critical for battery lifetime and aging properties. A common strategy to mitigate electrode mechanical degradation is to suppress the volume variation induced by Li/Na intercalation/deintercalation, thereby designing strain-less electrodes. In this study, we investigate the electrochemically-induced volume variation in layered and spinel compounds used in Li-ion and Na-ion battery electrode materials through density functional theory computations. Specifically, we propose to decompose the volume variation into electronic, ionic, and structural contributions. Based on this analysis, we suggest methods to separately influence each contribution through strategies such as chemical substitution, doping, and polymorphism. Altogether, we conclude that volume variations can be controlled by designing either mechanically hard or compact electrode materials. Full article
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<p>Relaxed volume per MO<math display="inline"><semantics> <msub> <mo>​</mo> <mn>2</mn> </msub> </semantics></math> stoichiometry of layered LiMO<math display="inline"><semantics> <msub> <mo>​</mo> <mn>2</mn> </msub> </semantics></math> and NaMO<math display="inline"><semantics> <msub> <mo>​</mo> <mn>2</mn> </msub> </semantics></math> (<b>a</b>) materials for different 3<span class="html-italic">d</span> transition metals ranging from Ti to Ni. Results are given for the lowest energy spin configuration obtained using different functionals, namey PBE + U (green symbols), PBE + U + D3 (orange symbols) and SCAN-rVV10 (blue symbols) compared with experimental data obtained from the literature (black symbols). Filled and open symbols correspond to the HS and LS states respectively. Tabulated ionic volume (<b>b</b>) for the LS and HS configurations of the different 3<span class="html-italic">d</span> transition metals in their +III state and in an octahedral environment. In (<b>c</b>) is shown the correlation between the relaxed volume of LiMO<math display="inline"><semantics> <msub> <mo>​</mo> <mn>2</mn> </msub> </semantics></math> (circles) and NaMO<math display="inline"><semantics> <msub> <mo>​</mo> <mn>2</mn> </msub> </semantics></math> (triangles) with the ionic volume computed using tabulated ionic radii (see text for details). Lines are guides for the eyes.</p>
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<p>(<b>a</b>) Relaxed volume per MO<math display="inline"><semantics> <msub> <mo>​</mo> <mn>2</mn> </msub> </semantics></math> unit of deintercalated MO<math display="inline"><semantics> <msub> <mo>​</mo> <mn>2</mn> </msub> </semantics></math> for the layered (circle) and spinel (square) polymorphs for different 3<span class="html-italic">d</span> transition metals ranging from Ti to Ni. Results are given for the lower energy spin configuration obtained using different functionals, namely PBE + U (green symbol), PBE + U + D3 (orange symbols) and SCAN-rVV10 (blue symbols) also compared with experimental volumes obtained from the literature. Color and symbol codes are consistent in all subfigures. (<b>b</b>) Tabulated ionic values of the TM’s in their +IV state in an octahedral environment. Hatched values for Fe and Co are calculated from the interpolation between Mn and Ni. (<b>c</b>) The correlation between the relaxed volume of MO<math display="inline"><semantics> <msub> <mo>​</mo> <mn>2</mn> </msub> </semantics></math> and the ionic volume was computed using tabulated ionic radii. In (<b>a</b>–<b>c</b>) lines are guides for the eyes, and results are given for the LS/HS configuration leading to the minimum energy. (<b>d</b>) Relative difference (in %) between relaxed and experimental cell parameters [<a href="#B57-batteries-10-00262" class="html-bibr">57</a>,<a href="#B58-batteries-10-00262" class="html-bibr">58</a>,<a href="#B59-batteries-10-00262" class="html-bibr">59</a>,<a href="#B60-batteries-10-00262" class="html-bibr">60</a>] a and c for layered materials. The dashed lines represent the mean relative error for each functional.</p>
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<p>Electrochemically-induced volume variation <math display="inline"><semantics> <mrow> <mo>????</mo> <mi>V</mi> <mo>/</mo> <mo>????</mo> <msub> <mi>n</mi> <mi mathvariant="normal">A</mi> </msub> </mrow> </semantics></math> in the lithiated (<b>a</b>), sodiated (<b>b</b>) layered structures and for lithiated spinel (<b>c</b>) structure as a function of the transition metal ranging from Ti to Ni. Results are given for the PBE + U + D3 (orange symbols) and SCAN-rVV10 functionals (blue symbols). Tabulated ionic volume difference (<b>d</b>) between the +IV and +III (HS/LS) states. For all subfigures, filled (open) symbols highlight cases for which the intercalated compound is the most stable within the HS (LS) configuration, respectively. Lines are guides for the eyes.</p>
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<p>Difference of electrochemically-induced volume variation (<b>a</b>) between the sodiated and lithiated layered materials as a function of the TM for the SCAN-rVV10 (blue circles) and PBE + U + D3 (orange circles) functionals. Ionic contribution (<b>b</b>) of the electrochemically-induced volume variation <math display="inline"><semantics> <mrow> <mo>????</mo> <msup> <mi>V</mi> <mi>Ionic</mi> </msup> <mo>/</mo> <mo>????</mo> <msub> <mi>n</mi> <mi mathvariant="normal">A</mi> </msub> </mrow> </semantics></math> as defined in Equation (<a href="#FD4-batteries-10-00262" class="html-disp-formula">4</a>) as a function of the TM for layered lithiated (blue circles), sodiated (orange triangles) and lithiated spinel (green squares) materials using the PBE + U + D3 functional. Filled and open symbols correspond to the HS and LS states respectively.</p>
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<p>Electronic contribution (<b>a</b>) of the electrochemically-induced volume variation as defined in Equation (<a href="#FD4-batteries-10-00262" class="html-disp-formula">4</a>) as a function of the TM for layered lithiated (blue circle), sodiated (orange triangle) and lithiated spinel (green square) materials using the PBE + U + D3 functional. Lines are guides for the eyes. (<b>b</b>) Relation between the electronic part of the total electrochemically-induced strain as a function of the inverse of the Bulk modulus. In all subfigures, filled (Open) symbols correspond to cases where the intercalated compound is in the HS (LS) configuration, respectively.</p>
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<p>Structural (Host) contribution (<b>a</b>) to the electrochemically-induced volume variation as defined in Equation (<a href="#FD4-batteries-10-00262" class="html-disp-formula">4</a>) as a function of the TM for layered lithiated (blue circle), sodiated (orange triangle) and lithiated spinel (green square) materials using the PBE + U + D3 functional. Filled and open symbols correspond to the HS and LS states respectively. (<b>b</b>) Structural (Host) contribution to the electrochemically-induced volume variation as a function of the total electrochemically-induced volume variation. (<b>c</b>) Electrochemically-induced volume variation as a function of the inverse of the elastic contant C<math display="inline"><semantics> <msub> <mo>​</mo> <mn>33</mn> </msub> </semantics></math>. In all subfigures, filled (Open) symbols correspond to cases where the intercalated compound is in the HS (LS) configuration, respectively. Lines are guides for the eyes.</p>
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20 pages, 18246 KiB  
Article
Investigation of High-Temperature Oxidation Behavior of Additive Manufactured CoCrMo Alloy for Mandrel Manufacturing
by Adina Cristina Toma, Mihaela Raluca Condruz, Alexandru Paraschiv, Teodor Adrian Badea, Delia Pătroi and Nicoleta Mirela Popa
Materials 2024, 17(15), 3660; https://doi.org/10.3390/ma17153660 - 24 Jul 2024
Viewed by 432
Abstract
The cyclic oxidation behavior of an additive manufactured CoCrMo alloy with 0.14 wt.% C was investigated at 914 °C for 32 cycles, each lasting 10 h, resulting in a total exposure time of 320 h. The oxidation rate was assessed for mass gain [...] Read more.
The cyclic oxidation behavior of an additive manufactured CoCrMo alloy with 0.14 wt.% C was investigated at 914 °C for 32 cycles, each lasting 10 h, resulting in a total exposure time of 320 h. The oxidation rate was assessed for mass gain after finishing each 40 h oxidation cycle. It was experimentally determined that the oxidative process at 914 °C of this CoCrMo alloy follows a parabolic law, with the process being fast at the beginning and slowing down after the first 40 h. The microstructural analysis revealed that in the as-printed state, the phases developed were primarily the γ matrix and minor traces of ε phase. The oxidative process ensured an increase in the ε phase and precipitation of carbides which produced a 12% increase in the material’s hardness after the first 40 h of exposure at 914 °C. The oxidation process led to the development of an oxide scale comprising a dense Cr2O3 layer and a porous layer of CoCr2O4 spinel, the latter spalling after the 240 h of exposure. Despite this spallation, the oxide scale continued to develop in the presence of O, Cr, and Co. The experimental analysis provided valuable insights regarding the material’s behavior under prolonged exposure at high temperature in air, demonstrating its suitability as a candidate for additive manufactured mandrels used for bending metallic pipe fitting elbows. Full article
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<p>Kinetic curve of CoCr oxidation at 914 °C for 320 h of maintaining.</p>
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<p>The mass gain rate of the oxidized specimens from additively manufactured CoCrMo as a function of time.</p>
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<p>Representative SEM images presenting the morphology evolution of the oxide scale over 320 h of isothermal oxidation of CoCrMo at 914 °C.</p>
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<p>Resulting XRD patterns for the CoCrMo reference and CoCrMo specimens exposed at 914 °C for various durations.</p>
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<p>The micro-areas where the SEM-EDS analysis was performed (marked in yellow squares).</p>
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<p>The micro-areas where the SEM-EDS analysis was performed (marked in yellow squares).</p>
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<p>The evolution of O, Cr, and Co wt.% content in the top surface of the oxide scale.</p>
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<p>The evolution of O, Cr, and Co content in the base of the oxide scale.</p>
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<p>The evolution of O, Cr, and Co content in the substrate (the base material).</p>
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<p>Oxide scale thickness as a function of time (SEM images with the oxide layer were made at a 5000× magnification).</p>
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<p>Representative optical microscopy images revealing the microstructural features of CoCrMo alloy in the as-printed state (magnification 200×, respective 500×).</p>
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<p>Representative optical microscopy images revealing the microstructural features of CoCrMo alloy after the isothermal oxidation cycles.</p>
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<p>Representative optical microscopy images revealing the microstructural features of CoCrMo alloy after the isothermal oxidation cycles.</p>
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<p>Representative optical microscopy images revealing the microstructural features of CoCrMo alloy after the isothermal oxidation cycles.</p>
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<p>Hardness evolution of additive manufactured CoCrMo alloy.</p>
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16 pages, 3699 KiB  
Article
Morphology Modulation of ZnMn2O4 Nanoparticles Deposited In Situ on Carbon Cloth for Supercapacitors
by Changxing Li, Xuansheng Feng, Jixue Zhou, Guochen Zhao, Kaiming Cheng, Huan Yu, Hang Li, Huabing Yang, Dongqing Zhao and Xitao Wang
Metals 2024, 14(8), 841; https://doi.org/10.3390/met14080841 - 23 Jul 2024
Viewed by 583
Abstract
As a typical spinel structure material, ZnMn2O4 has been widely researched in the field of electrode materials. However, ZnMn2O4 nanoparticles as electrode materials for supercapacitors have the disadvantages of low conductivity, inferior structural integrity, and easy aggregation, [...] Read more.
As a typical spinel structure material, ZnMn2O4 has been widely researched in the field of electrode materials. However, ZnMn2O4 nanoparticles as electrode materials for supercapacitors have the disadvantages of low conductivity, inferior structural integrity, and easy aggregation, resulting in unsatisfying electrochemical performance. In this work, we use a hydrothermal method and high-temperature calcination to deposit ZnMn2O4 nanoparticles on carbon cloth and explore the influence of hydrothermal reaction time on the deposition morphology and distribution of ZnMn2O4 nanoparticles on carbon cloth. The deposition process of ZnMn2O4 nanoparticles on carbon cloth was analyzed, and a ZMO-9 electrode was deduced to be the most suitable electrode for supercapacitors. A series of electrochemical performance tests show that the ZMO-9 electrode has excellent specific capacitance (specific capacity) (499 F·g−1 (299.4 C·g−1) at a current density of 1 A·g−1) and rate performance (75% capacitance retention at a current density of 12 A·g−1). The assembled asymmetric supercapacitor has an energy density of 46.6 Wh·kg−1 when the power density is 800.1 W·kg−1. This work provides a reference for the structural design of ZnMn2O4 supercapacitor electrode materials and the improvement of electrochemical properties. Full article
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<p>(<b>a</b>) XRD patterns of the as-prepared samples. (<b>b</b>) XPS full scan spectra, (<b>c</b>) Zn 2p, and (<b>d</b>) Mn 2p spectra of ZnMn<sub>2</sub>O<sub>4</sub>.</p>
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<p>SEM images of ZnMn<sub>2</sub>O<sub>4</sub> with different hydrothermal reaction times: hydrothermal reaction times of 7 h (<b>a</b>–<b>c</b>), 9 h (<b>d</b>–<b>f</b>), and 12 h (<b>g</b>–<b>i</b>).</p>
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<p>TEM images of ZnMn<sub>2</sub>O<sub>4</sub> with different hydrothermal reaction times: hydrothermal reaction time of 7 h (<b>a</b>,<b>b</b>,<b>e</b>,<b>f</b>,<b>i</b>,<b>j</b>), 9 h (<b>c</b>,<b>g</b>,<b>k</b>), and 12 h (<b>d</b>,<b>h</b>,<b>l</b>).</p>
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<p>Schematic illustration of the fabrication process of ZnMn<sub>2</sub>O<sub>4</sub>@carbon cloth.</p>
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<p>(<b>a</b>) CV curves at the scan rate of 5 mV·s<sup>−1</sup>. (<b>b</b>) CV curves of the ZMO-9 electrode at a scan rate of 5 mV·s<sup>−1</sup> to 90 mV·s<sup>−1</sup>. (<b>c</b>) GCD curves at a current density of 1 A·g<sup>−1</sup>. (<b>d</b>) GCD curves at different current densities of the ZMO-9 electrode. (<b>e</b>) Comparison of the specific capacitance change. (<b>f</b>) The fitting EIS curves of the ZMO-7, ZMO-9 and ZMO-12 electrodes.</p>
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<p>(<b>a</b>) Determination of the b-value from the anodic and cathode peak currents using the power law. (<b>b</b>) Capacitance contribution at 10 mV·s<sup>−1</sup>. (<b>c</b>) The capacitance contribution ratio at different scan rates. (<b>d</b>) Long-cycle performance of the ZMO-7, ZMO-9, and ZMO-12 electrodes at 1 A·g<sup>−1</sup>. (<b>e</b>) Diagram of contact between the electrolytes and electrode materials.</p>
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<p>(<b>a</b>) A schematic diagram of the ZMO-9//AC device. (<b>b</b>) CV curves of the ZMO-9//AC device with scan rates ranging from 10 to 100 mV·s<sup>−1</sup>. (<b>c</b>) GCD curves at various current densities. (<b>d</b>) The specific capacitance at various current densities. (<b>e</b>) The cycling stability of the ZMO-9//AC device. (<b>f</b>) The energy and power densities of the ZMO-9//AC device and other devices [<a href="#B39-metals-14-00841" class="html-bibr">39</a>,<a href="#B50-metals-14-00841" class="html-bibr">50</a>,<a href="#B51-metals-14-00841" class="html-bibr">51</a>,<a href="#B52-metals-14-00841" class="html-bibr">52</a>,<a href="#B53-metals-14-00841" class="html-bibr">53</a>,<a href="#B54-metals-14-00841" class="html-bibr">54</a>,<a href="#B55-metals-14-00841" class="html-bibr">55</a>,<a href="#B56-metals-14-00841" class="html-bibr">56</a>].</p>
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10 pages, 7696 KiB  
Article
A Novel Spinel High-Entropy Oxide (Cr0.2Mn0.2Co0.2Ni0.2Zn0.2)3O4 as Anode Material for Lithium-Ion Batteries
by Changqing Jin, Yulong Wang, Haobin Dong, Yongxing Wei, Ruihua Nan, Zengyun Jian, Zhong Yang and Qingping Ding
Inorganics 2024, 12(7), 198; https://doi.org/10.3390/inorganics12070198 - 21 Jul 2024
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Abstract
In this study, we synthesized spinel high-entropy oxide (HEO) (Cr0.2Mn0.2Co0.2Ni0.2Zn0.2)3O4 nanoparticles by a simple solution combustion method. These particles were investigated for their performance as anodes in lithium-ion batteries. The [...] Read more.
In this study, we synthesized spinel high-entropy oxide (HEO) (Cr0.2Mn0.2Co0.2Ni0.2Zn0.2)3O4 nanoparticles by a simple solution combustion method. These particles were investigated for their performance as anodes in lithium-ion batteries. The reversible capacity is 132 mAh·g−1 after 100 cycles at a current density of 100 mA·g−1, 107 mAh·g−1 after 1000 cycles at a current density of 1 A g−1, and 96 mAh·g−1 rate capacity at a high current density of 2 A g−1. The outstanding cycle stability under high current densities and remarkable rate performance can be attributed to the stable structure originating from the high entropy of the material. Full article
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Figure 1

Figure 1
<p>(<b>a</b>) XRD pattern; (<b>b</b>) Rietveld refinement pattern of the (Cr<sub>0.2</sub>Mn<sub>0.2</sub>Co<sub>0.2</sub>Ni<sub>0.2</sub>Zn<sub>0.2</sub>)<sub>3</sub>O<sub>4</sub> nanoparticles.</p>
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<p>SEM image (<b>a</b>) and corresponding EDS elemental maps of Cr (<b>b</b>), Mn (<b>c</b>), Co (<b>d</b>), Ni (<b>e</b>), and Zn (<b>f</b>), and TEM image (<b>g</b>) of (Cr<sub>0.2</sub>Mn<sub>0.2</sub>Co<sub>0.2</sub>Ni<sub>0.2</sub>Zn<sub>0.2</sub>)<sub>3</sub>O<sub>4</sub> nanoparticles. The inset in (<b>g</b>) shows the distribution of the particle size.</p>
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<p>CV curves at a scan rate of 0. 1 mV·s<sup>−1</sup> (<b>a</b>), discharge/charge profiles at 100 mA·g<sup>−1</sup> (<b>b</b>), cycling performance at 100 mA·g<sup>−1</sup> (<b>c</b>), long-term cycling performance at 1 A g<sup>−1</sup> (<b>d</b>), and rate capability of (Cr<sub>0.2</sub>Mn<sub>0.2</sub>Co<sub>0.2</sub>Ni<sub>0.2</sub>Zn<sub>0.2</sub>)<sub>3</sub>O<sub>4</sub> electrode (<b>e</b>).</p>
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<p>EIS plots of HEO electrode before (HEO-0) and after 20 cycles (HEO-20) at 0.1 A g<sup>−1</sup>.</p>
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<p>XPS spectra of Co 2p (<b>a</b>) and Ni 2p (<b>c</b>) of HEO before cycling and XPS spectra of Co 2p (<b>b</b>) and Ni 2p (<b>d</b>) of HEO after 1000 cycles at 1 A g<sup>−1</sup>.</p>
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<p>SEM image of HEO before (<b>a</b>) and after (<b>b</b>) 1000 cycles at a current density of 1 A g<sup>−1</sup>; corresponding elemental mapping of all elements (<b>c</b>), and corresponding elemental mapping of Cr (<b>d</b>), Mn (<b>e</b>), Co (<b>f</b>), Ni (<b>g</b>), and Zn (<b>h</b>) of the HEO.</p>
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