Debye Temperature Evaluation for Secondary Battery Cathode of α-Sn<i><sub>x</sub></i>Fe<sub>1−<i>x</i></sub>OOH Nanoparticles Derived from the <sup>57</sup>Fe- and <sup>119</sup>Sn-Mössbauer Spectra
Debye temperatures of <i>α</i>-Sn<i><sub>x</sub></i>Fe<sub>1−<i>x</i></sub>OOH nanoparticles (<i>x</i> = 0, 0.05, 0.10, 0.15 and 0.20, abbreviated as Sn100<i>x</i> NPs) prepared by hydrothermal reaction were estimate...
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2024-02-01
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| author | Ahmed Ibrahim Kaoru Tani Kanae Hashi Bofan Zhang Zoltán Homonnay Ernő Kuzmann Arijeta Bafti Luka Pavić Stjepko Krehula Marijan Marciuš Shiro Kubuki |
| author_facet | Ahmed Ibrahim Kaoru Tani Kanae Hashi Bofan Zhang Zoltán Homonnay Ernő Kuzmann Arijeta Bafti Luka Pavić Stjepko Krehula Marijan Marciuš Shiro Kubuki |
| author_sort | Ahmed Ibrahim |
| collection | DOAJ |
| description | Debye temperatures of <i>α</i>-Sn<i><sub>x</sub></i>Fe<sub>1−<i>x</i></sub>OOH nanoparticles (<i>x</i> = 0, 0.05, 0.10, 0.15 and 0.20, abbreviated as Sn100<i>x</i> NPs) prepared by hydrothermal reaction were estimated with <sup>57</sup>Fe- and <sup>119</sup>Sn-Mössbauer spectra measured by varying the temperature from 20 to 300 K. Electrical properties were studied by solid-state impedance spectroscopy (SS-IS). Together, the charge–discharge capacity of Li- and Na-ion batteries containing Sn100<i>x</i> NPs as a cathode were evaluated. <sup>57</sup>Fe-Mössbauer spectra of Sn10, Sn15, and Sn20 measured at 300 K showed only one doublet due to the superparamagnetic doublet, while the doublet decomposed into a sextet due to goethite at the temperature below 50 K for Sn 10, 200 K for Sn15, and 100 K for Sn20. These results suggest that Sn10, Sn15 and Sn20 had smaller particles than Sn0. On the other hand, 20 K <sup>119</sup>Sn-Mössbauer spectra of Sn15 were composed of a paramagnetic doublet with an isomer shift (<i>δ</i>) of 0.24 mm s<sup>−1</sup> and quadrupole splitting (∆) of 3.52 mm s<sup>−1</sup>. These values were larger than those of Sn10 (<i>δ</i>: 0.08 mm s<sup>−1</sup>, ∆: 0.00 mm s<sup>−1</sup>) and Sn20 (<i>δ</i>: 0.10 mm s<sup>−1</sup>, ∆: 0.00 mm s<sup>−1</sup>), suggesting that the Sn<sup>IV</sup>-O chemical bond is shorter and the distortion of octahedral SnO<sub>6</sub> is larger in Sn15 than in Sn10 and Sn20 due to the increase in the covalency and polarization of the Sn<sup>IV</sup>-O chemical bond. Debye temperatures determined from <sup>57</sup>Fe-Mössbauer spectra measured at the low temperature were 210 K, 228 K, and 250 K for Sn10, Sn15, and Sn20, while that of <i>α</i>-Fe<sub>2</sub>O<sub>3</sub> was 324 K. Similarly, the Debye temperature of 199, 251, and 269 K for Sn10, Sn15, and Sn20 were estimated from the temperature-dependent <sup>119</sup>Sn-Mössbauer spectra, which were significantly smaller than that of BaSnO<sub>3</sub> (=658 K) and SnO<sub>2</sub> (=382 K). These results suggest that Fe and Sn are a weakly bound lattice in goethite NPs with low crystallinity. Modification of NPs and addition of Sn has a positive effect, resulting in an increase in DC conductivity of almost 5 orders of magnitude, from a <i>σ</i><sub>DC</sub> value of 9.37 × 10<sup>−7</sup> (Ω cm)<sup>−1</sup> for pure goethite Sn (Sn0) up to DC plateau for samples containing 0.15 and 0.20 Sn (Sn15 and Sn20) with a DC value of ~4 × 10<sup>−7</sup> (Ω cm)<sup>−1</sup> @423 K. This non-linear conductivity pattern and levelling at a higher Sn content suggests that structural modifications have a notable impact on electron transport, which is primarily governed by the thermally activated via three-dimensional hopping of small polarons (SPH). Measurements of SIB performance, including the Sn100<i>x</i> cathode under a current density of 50 mA g<sup>−1</sup>, showed initial capacities of 81 and 85 mAh g<sup>−1</sup> for Sn0 and Sn15, which were larger than the others. The large initial capacities were measured at a current density of 5 mA g<sup>−1</sup> found at 170 and 182 mAh g<sup>−1</sup> for Sn15 and Sn20, respectively. It is concluded that tin-goethite NPs are an excellent material for a secondary battery cathode and that Sn15 is the best cathode among the studied Sn100<i>x</i> NPs. |
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| spelling | doaj.art-5e829df5e4464232b47361882d94c0c12024-03-12T16:45:09ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672024-02-01255248810.3390/ijms25052488Debye Temperature Evaluation for Secondary Battery Cathode of α-Sn<i><sub>x</sub></i>Fe<sub>1−<i>x</i></sub>OOH Nanoparticles Derived from the <sup>57</sup>Fe- and <sup>119</sup>Sn-Mössbauer SpectraAhmed Ibrahim0Kaoru Tani1Kanae Hashi2Bofan Zhang3Zoltán Homonnay4Ernő Kuzmann5Arijeta Bafti6Luka Pavić7Stjepko Krehula8Marijan Marciuš9Shiro Kubuki10Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, Tokyo 192-0397, JapanDepartment of Chemistry, Graduate School of Science, Tokyo Metropolitan University, Tokyo 192-0397, JapanDepartment of Chemistry, Graduate School of Science, Tokyo Metropolitan University, Tokyo 192-0397, JapanDepartment of Chemistry, Graduate School of Science, Tokyo Metropolitan University, Tokyo 192-0397, JapanInstitute of Chemistry, Eötvos Loránd University, 1117 Budapest, HungaryInstitute of Chemistry, Eötvos Loránd University, 1117 Budapest, HungaryFaculty of Chemical Engineering and Technology, University of Zagreb, 10000 Zagreb, CroatiaDivision of Materials Chemistry, Ruđer Bošković Institute, 10000 Zagreb, CroatiaDivision of Materials Chemistry, Ruđer Bošković Institute, 10000 Zagreb, CroatiaDivision of Materials Chemistry, Ruđer Bošković Institute, 10000 Zagreb, CroatiaDepartment of Chemistry, Graduate School of Science, Tokyo Metropolitan University, Tokyo 192-0397, JapanDebye temperatures of <i>α</i>-Sn<i><sub>x</sub></i>Fe<sub>1−<i>x</i></sub>OOH nanoparticles (<i>x</i> = 0, 0.05, 0.10, 0.15 and 0.20, abbreviated as Sn100<i>x</i> NPs) prepared by hydrothermal reaction were estimated with <sup>57</sup>Fe- and <sup>119</sup>Sn-Mössbauer spectra measured by varying the temperature from 20 to 300 K. Electrical properties were studied by solid-state impedance spectroscopy (SS-IS). Together, the charge–discharge capacity of Li- and Na-ion batteries containing Sn100<i>x</i> NPs as a cathode were evaluated. <sup>57</sup>Fe-Mössbauer spectra of Sn10, Sn15, and Sn20 measured at 300 K showed only one doublet due to the superparamagnetic doublet, while the doublet decomposed into a sextet due to goethite at the temperature below 50 K for Sn 10, 200 K for Sn15, and 100 K for Sn20. These results suggest that Sn10, Sn15 and Sn20 had smaller particles than Sn0. On the other hand, 20 K <sup>119</sup>Sn-Mössbauer spectra of Sn15 were composed of a paramagnetic doublet with an isomer shift (<i>δ</i>) of 0.24 mm s<sup>−1</sup> and quadrupole splitting (∆) of 3.52 mm s<sup>−1</sup>. These values were larger than those of Sn10 (<i>δ</i>: 0.08 mm s<sup>−1</sup>, ∆: 0.00 mm s<sup>−1</sup>) and Sn20 (<i>δ</i>: 0.10 mm s<sup>−1</sup>, ∆: 0.00 mm s<sup>−1</sup>), suggesting that the Sn<sup>IV</sup>-O chemical bond is shorter and the distortion of octahedral SnO<sub>6</sub> is larger in Sn15 than in Sn10 and Sn20 due to the increase in the covalency and polarization of the Sn<sup>IV</sup>-O chemical bond. Debye temperatures determined from <sup>57</sup>Fe-Mössbauer spectra measured at the low temperature were 210 K, 228 K, and 250 K for Sn10, Sn15, and Sn20, while that of <i>α</i>-Fe<sub>2</sub>O<sub>3</sub> was 324 K. Similarly, the Debye temperature of 199, 251, and 269 K for Sn10, Sn15, and Sn20 were estimated from the temperature-dependent <sup>119</sup>Sn-Mössbauer spectra, which were significantly smaller than that of BaSnO<sub>3</sub> (=658 K) and SnO<sub>2</sub> (=382 K). These results suggest that Fe and Sn are a weakly bound lattice in goethite NPs with low crystallinity. Modification of NPs and addition of Sn has a positive effect, resulting in an increase in DC conductivity of almost 5 orders of magnitude, from a <i>σ</i><sub>DC</sub> value of 9.37 × 10<sup>−7</sup> (Ω cm)<sup>−1</sup> for pure goethite Sn (Sn0) up to DC plateau for samples containing 0.15 and 0.20 Sn (Sn15 and Sn20) with a DC value of ~4 × 10<sup>−7</sup> (Ω cm)<sup>−1</sup> @423 K. This non-linear conductivity pattern and levelling at a higher Sn content suggests that structural modifications have a notable impact on electron transport, which is primarily governed by the thermally activated via three-dimensional hopping of small polarons (SPH). Measurements of SIB performance, including the Sn100<i>x</i> cathode under a current density of 50 mA g<sup>−1</sup>, showed initial capacities of 81 and 85 mAh g<sup>−1</sup> for Sn0 and Sn15, which were larger than the others. The large initial capacities were measured at a current density of 5 mA g<sup>−1</sup> found at 170 and 182 mAh g<sup>−1</sup> for Sn15 and Sn20, respectively. It is concluded that tin-goethite NPs are an excellent material for a secondary battery cathode and that Sn15 is the best cathode among the studied Sn100<i>x</i> NPs.https://www.mdpi.com/1422-0067/25/5/2488tin-goethite nanoparticleshydrothermal reactionMössbauer spectroscopysecondary battery cathode |
| spellingShingle | Ahmed Ibrahim Kaoru Tani Kanae Hashi Bofan Zhang Zoltán Homonnay Ernő Kuzmann Arijeta Bafti Luka Pavić Stjepko Krehula Marijan Marciuš Shiro Kubuki Debye Temperature Evaluation for Secondary Battery Cathode of α-Sn<i><sub>x</sub></i>Fe<sub>1−<i>x</i></sub>OOH Nanoparticles Derived from the <sup>57</sup>Fe- and <sup>119</sup>Sn-Mössbauer Spectra International Journal of Molecular Sciences tin-goethite nanoparticles hydrothermal reaction Mössbauer spectroscopy secondary battery cathode |
| title | Debye Temperature Evaluation for Secondary Battery Cathode of α-Sn<i><sub>x</sub></i>Fe<sub>1−<i>x</i></sub>OOH Nanoparticles Derived from the <sup>57</sup>Fe- and <sup>119</sup>Sn-Mössbauer Spectra |
| title_full | Debye Temperature Evaluation for Secondary Battery Cathode of α-Sn<i><sub>x</sub></i>Fe<sub>1−<i>x</i></sub>OOH Nanoparticles Derived from the <sup>57</sup>Fe- and <sup>119</sup>Sn-Mössbauer Spectra |
| title_fullStr | Debye Temperature Evaluation for Secondary Battery Cathode of α-Sn<i><sub>x</sub></i>Fe<sub>1−<i>x</i></sub>OOH Nanoparticles Derived from the <sup>57</sup>Fe- and <sup>119</sup>Sn-Mössbauer Spectra |
| title_full_unstemmed | Debye Temperature Evaluation for Secondary Battery Cathode of α-Sn<i><sub>x</sub></i>Fe<sub>1−<i>x</i></sub>OOH Nanoparticles Derived from the <sup>57</sup>Fe- and <sup>119</sup>Sn-Mössbauer Spectra |
| title_short | Debye Temperature Evaluation for Secondary Battery Cathode of α-Sn<i><sub>x</sub></i>Fe<sub>1−<i>x</i></sub>OOH Nanoparticles Derived from the <sup>57</sup>Fe- and <sup>119</sup>Sn-Mössbauer Spectra |
| title_sort | debye temperature evaluation for secondary battery cathode of α sn i sub x sub i fe sub 1 i x i sub ooh nanoparticles derived from the sup 57 sup fe and sup 119 sup sn mossbauer spectra |
| topic | tin-goethite nanoparticles hydrothermal reaction Mössbauer spectroscopy secondary battery cathode |
| url | https://www.mdpi.com/1422-0067/25/5/2488 |
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