Conversion of Li2FeSbO5 to the Fe(III)/Fe(V) phase LiFeSbO5 via topochemical lithium extraction
<p>Reaction between Na<sub>2</sub>FeSbO<sub>5</sub> and LiNO<sub>3</sub> at 300 °C yields the metastable phase Li<sub>2</sub>FeSbO<sub>5</sub> which is isostructural with the sodium “parent...
| Main Authors: | , , , , |
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| Format: | Journal article |
| Language: | English |
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American Chemical Society
2022
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| _version_ | 1797109381941166080 |
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| author | de Irujo-Labalde, XM Scrimshire, A Bingham, PA Suard, E Hayward, MA |
| author_facet | de Irujo-Labalde, XM Scrimshire, A Bingham, PA Suard, E Hayward, MA |
| author_sort | de Irujo-Labalde, XM |
| collection | OXFORD |
| description | <p>Reaction between Na<sub>2</sub>FeSbO<sub>5</sub> and LiNO<sub>3</sub> at 300 °C yields the metastable phase Li<sub>2</sub>FeSbO<sub>5</sub> which is isostructural with the sodium “parent” phase (space group <em>Pbna</em>, <em>a</em> = 15.138(1) Å, <em>b</em> = 5.1440(3) Å, <em>c</em> = 10.0936(6) Å) consisting of an alternating stack of Li<sub>2</sub>Fe<sub>2</sub>O<sub>5</sub> and Li<sub>2</sub>Sb<sub>2</sub>O<sub>5</sub> sheets containing tetrahedral coordinated Fe<sup>3+</sup> and octahedrally coordinated Sb<sup>5+</sup>, respectively. Further reaction between Li<sub>2</sub>FeSbO<sub>5</sub> with NO<sub>2</sub>BF<sub>4</sub> in acetonitrile at room temperature yields LiFeSbO<sub>5</sub>, which adopts an orthorhombic structure (space group <em>Pbn</em>2<sub>1</sub>, <em>a</em> = 14.2943(4) Å, <em>b</em> = 5.2771(1) Å, <em>c</em> = 9.5610(3) Å) in which the LiFeO<sub>5</sub> layers have shifted on lithium extraction, resulting in an octahedral coordination for the iron cations. <sup>57</sup>Fe Mössbauer data indicate that the nominal Fe<sup>4+</sup> cations present in LiFeSbO<sub>5</sub> have disproportionated into a 1:1 combination of Fe<sup>3+</sup> and Fe<sup>5+</sup> centers which are ordered within the LiFeSbO<sub>5</sub> structural framework. It is widely observed that Fe<sup>4+</sup> centers tend to be unstable in delithiated Li–Fe–X–O phases currently proposed as lithium-ion battery cathode materials, so the apparent stability of highly oxidized Fe<sup>5+</sup> centers in LiFeSbO<sub>5</sub> is notable, suggesting cathode materials based on oxidizing Fe<sup>3+</sup> could be possible. However, in this instance, the structural change which occurs on delithiation of Li<sub>2</sub>FeSbO<sub>5</sub> prevents electrochemical cycling of this material.</p> |
| first_indexed | 2024-03-07T07:41:07Z |
| format | Journal article |
| id | oxford-uuid:8d8670d3-0a9e-438a-bc1e-292c9921de00 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T07:41:07Z |
| publishDate | 2022 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:8d8670d3-0a9e-438a-bc1e-292c9921de002023-04-24T07:51:40ZConversion of Li2FeSbO5 to the Fe(III)/Fe(V) phase LiFeSbO5 via topochemical lithium extractionJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:8d8670d3-0a9e-438a-bc1e-292c9921de00EnglishSymplectic ElementsAmerican Chemical Society2022de Irujo-Labalde, XMScrimshire, ABingham, PASuard, EHayward, MA<p>Reaction between Na<sub>2</sub>FeSbO<sub>5</sub> and LiNO<sub>3</sub> at 300 °C yields the metastable phase Li<sub>2</sub>FeSbO<sub>5</sub> which is isostructural with the sodium “parent” phase (space group <em>Pbna</em>, <em>a</em> = 15.138(1) Å, <em>b</em> = 5.1440(3) Å, <em>c</em> = 10.0936(6) Å) consisting of an alternating stack of Li<sub>2</sub>Fe<sub>2</sub>O<sub>5</sub> and Li<sub>2</sub>Sb<sub>2</sub>O<sub>5</sub> sheets containing tetrahedral coordinated Fe<sup>3+</sup> and octahedrally coordinated Sb<sup>5+</sup>, respectively. Further reaction between Li<sub>2</sub>FeSbO<sub>5</sub> with NO<sub>2</sub>BF<sub>4</sub> in acetonitrile at room temperature yields LiFeSbO<sub>5</sub>, which adopts an orthorhombic structure (space group <em>Pbn</em>2<sub>1</sub>, <em>a</em> = 14.2943(4) Å, <em>b</em> = 5.2771(1) Å, <em>c</em> = 9.5610(3) Å) in which the LiFeO<sub>5</sub> layers have shifted on lithium extraction, resulting in an octahedral coordination for the iron cations. <sup>57</sup>Fe Mössbauer data indicate that the nominal Fe<sup>4+</sup> cations present in LiFeSbO<sub>5</sub> have disproportionated into a 1:1 combination of Fe<sup>3+</sup> and Fe<sup>5+</sup> centers which are ordered within the LiFeSbO<sub>5</sub> structural framework. It is widely observed that Fe<sup>4+</sup> centers tend to be unstable in delithiated Li–Fe–X–O phases currently proposed as lithium-ion battery cathode materials, so the apparent stability of highly oxidized Fe<sup>5+</sup> centers in LiFeSbO<sub>5</sub> is notable, suggesting cathode materials based on oxidizing Fe<sup>3+</sup> could be possible. However, in this instance, the structural change which occurs on delithiation of Li<sub>2</sub>FeSbO<sub>5</sub> prevents electrochemical cycling of this material.</p> |
| spellingShingle | de Irujo-Labalde, XM Scrimshire, A Bingham, PA Suard, E Hayward, MA Conversion of Li2FeSbO5 to the Fe(III)/Fe(V) phase LiFeSbO5 via topochemical lithium extraction |
| title | Conversion of Li2FeSbO5 to the Fe(III)/Fe(V) phase LiFeSbO5 via topochemical lithium extraction |
| title_full | Conversion of Li2FeSbO5 to the Fe(III)/Fe(V) phase LiFeSbO5 via topochemical lithium extraction |
| title_fullStr | Conversion of Li2FeSbO5 to the Fe(III)/Fe(V) phase LiFeSbO5 via topochemical lithium extraction |
| title_full_unstemmed | Conversion of Li2FeSbO5 to the Fe(III)/Fe(V) phase LiFeSbO5 via topochemical lithium extraction |
| title_short | Conversion of Li2FeSbO5 to the Fe(III)/Fe(V) phase LiFeSbO5 via topochemical lithium extraction |
| title_sort | conversion of li2fesbo5 to the fe iii fe v phase lifesbo5 via topochemical lithium extraction |
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