Structure Evolution of Na2O2 from Room Temperature to 500 °C
Na2O2 is one of the possible discharge products from sodium–air batteries. Here, we report the evolution of the structure of Na2O2 from room temperature to 500 °C using variable-temperature neutron and synchrotron X-ray powder diffraction. A phase transition from α-Na2O2 to β-Na2O2 is observed in th...
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Veröffentlicht in: | Inorganic chemistry 2020-10, Vol.59 (19), p.14439-14446 |
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description | Na2O2 is one of the possible discharge products from sodium–air batteries. Here, we report the evolution of the structure of Na2O2 from room temperature to 500 °C using variable-temperature neutron and synchrotron X-ray powder diffraction. A phase transition from α-Na2O2 to β-Na2O2 is observed in the neutron diffraction measurements above 400 °C, and the crystal structure of β-Na2O2 is determined from neutron diffraction data at 500 °C. α-Na2O2 adapts a hexagonal P 62m (no. 189) structure, and β-Na2O2 adapts a tetragonal I41/acd (no. 142) structure. The thermal expansion coefficients of α-Na2O2 are a = 2.98(1) × 10–5 K–1, c = 2.89(1) × 10–5 K–1, and V = 8.96(1) × 10–5 K–1 up to 400 °C, and a ∼10% volume expansion occurs during the phase transition from α-Na2O2 to β-Na2O2 due to the realignment/rotation of O2 2– groups. Both phases are electronic insulators according to DFT calculations with band gaps (both indirect) of 1.75 eV (α-Na2O2) and 2.56 eV (β-Na2O2). An impedance analysis from room temperature to 400 °C revealed a significant enhancement of the conductivity at T ≥ 275 °C. α-Na2O2 shows a higher conductivity (∼10 times at T ≤ 275 °C and ∼3 times at T > 275 °C) in O2 compared to in Ar. We confirmed, by dielectric analysis, that this enhanced conductivity is dominated by ionic conduction. |
doi_str_mv | 10.1021/acs.inorgchem.0c02234 |
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Here, we report the evolution of the structure of Na2O2 from room temperature to 500 °C using variable-temperature neutron and synchrotron X-ray powder diffraction. A phase transition from α-Na2O2 to β-Na2O2 is observed in the neutron diffraction measurements above 400 °C, and the crystal structure of β-Na2O2 is determined from neutron diffraction data at 500 °C. α-Na2O2 adapts a hexagonal P 62m (no. 189) structure, and β-Na2O2 adapts a tetragonal I41/acd (no. 142) structure. The thermal expansion coefficients of α-Na2O2 are a = 2.98(1) × 10–5 K–1, c = 2.89(1) × 10–5 K–1, and V = 8.96(1) × 10–5 K–1 up to 400 °C, and a ∼10% volume expansion occurs during the phase transition from α-Na2O2 to β-Na2O2 due to the realignment/rotation of O2 2– groups. Both phases are electronic insulators according to DFT calculations with band gaps (both indirect) of 1.75 eV (α-Na2O2) and 2.56 eV (β-Na2O2). An impedance analysis from room temperature to 400 °C revealed a significant enhancement of the conductivity at T ≥ 275 °C. α-Na2O2 shows a higher conductivity (∼10 times at T ≤ 275 °C and ∼3 times at T > 275 °C) in O2 compared to in Ar. We confirmed, by dielectric analysis, that this enhanced conductivity is dominated by ionic conduction.</description><identifier>ISSN: 0020-1669</identifier><identifier>EISSN: 1520-510X</identifier><identifier>DOI: 10.1021/acs.inorgchem.0c02234</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Inorganic chemistry, 2020-10, Vol.59 (19), p.14439-14446</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><orcidid>0000-0003-2366-5809 ; 0000-0003-2205-3106 ; 0000-0001-5527-199X ; 0000-0002-7187-4579</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.0c02234$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.0c02234$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,27076,27924,27925,56738,56788</link.rule.ids></links><search><creatorcontrib>Wang, Chun-Hai</creatorcontrib><creatorcontrib>Gui, Dong-Yun</creatorcontrib><creatorcontrib>Xia, Qingbo</creatorcontrib><creatorcontrib>Avdeev, Maxim</creatorcontrib><creatorcontrib>Ling, Chris D</creatorcontrib><creatorcontrib>Kennedy, Brendan J</creatorcontrib><title>Structure Evolution of Na2O2 from Room Temperature to 500 °C</title><title>Inorganic chemistry</title><addtitle>Inorg. Chem</addtitle><description>Na2O2 is one of the possible discharge products from sodium–air batteries. Here, we report the evolution of the structure of Na2O2 from room temperature to 500 °C using variable-temperature neutron and synchrotron X-ray powder diffraction. A phase transition from α-Na2O2 to β-Na2O2 is observed in the neutron diffraction measurements above 400 °C, and the crystal structure of β-Na2O2 is determined from neutron diffraction data at 500 °C. α-Na2O2 adapts a hexagonal P 62m (no. 189) structure, and β-Na2O2 adapts a tetragonal I41/acd (no. 142) structure. The thermal expansion coefficients of α-Na2O2 are a = 2.98(1) × 10–5 K–1, c = 2.89(1) × 10–5 K–1, and V = 8.96(1) × 10–5 K–1 up to 400 °C, and a ∼10% volume expansion occurs during the phase transition from α-Na2O2 to β-Na2O2 due to the realignment/rotation of O2 2– groups. Both phases are electronic insulators according to DFT calculations with band gaps (both indirect) of 1.75 eV (α-Na2O2) and 2.56 eV (β-Na2O2). An impedance analysis from room temperature to 400 °C revealed a significant enhancement of the conductivity at T ≥ 275 °C. α-Na2O2 shows a higher conductivity (∼10 times at T ≤ 275 °C and ∼3 times at T > 275 °C) in O2 compared to in Ar. We confirmed, by dielectric analysis, that this enhanced conductivity is dominated by ionic conduction.</description><issn>0020-1669</issn><issn>1520-510X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNo9kMFKAzEQhoMoWKuPIOToZeskmWR3Dx6k1CoUC7oHbyFNs9qyu6nJrs_lM_hkprZ4mRn--RiGj5BrBhMGnN0aGyebzod3--HaCVjgXOAJGTHJIZMM3k7JCCDNTKnynFzEuAWAUqAakbvXPgy2H4Kjsy_fDP3Gd9TX9NnwJad18C198alUrt25YP7A3lMJQH--p5fkrDZNdFfHPibVw6yaPmaL5fxper_ITC5lti4KLNalZcgE5s5hnTMmc7SwUqYwuVuL0nBXKq5yAESZOJFWoAzWfAViTG4OZ3fBfw4u9rrdROuaxnTOD1FzRFTACy4Tyg5okqK3fghd-ksz0HtTeh_-m9JHU-IXPORdzQ</recordid><startdate>20201005</startdate><enddate>20201005</enddate><creator>Wang, Chun-Hai</creator><creator>Gui, Dong-Yun</creator><creator>Xia, Qingbo</creator><creator>Avdeev, Maxim</creator><creator>Ling, Chris D</creator><creator>Kennedy, Brendan J</creator><general>American Chemical Society</general><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-2366-5809</orcidid><orcidid>https://orcid.org/0000-0003-2205-3106</orcidid><orcidid>https://orcid.org/0000-0001-5527-199X</orcidid><orcidid>https://orcid.org/0000-0002-7187-4579</orcidid></search><sort><creationdate>20201005</creationdate><title>Structure Evolution of Na2O2 from Room Temperature to 500 °C</title><author>Wang, Chun-Hai ; Gui, Dong-Yun ; Xia, Qingbo ; Avdeev, Maxim ; Ling, Chris D ; Kennedy, Brendan J</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a755-d8848d9c141347ee4f711574c0b6a8a7ed39a2e96267004454133b6a06a4f2b03</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Wang, Chun-Hai</creatorcontrib><creatorcontrib>Gui, Dong-Yun</creatorcontrib><creatorcontrib>Xia, Qingbo</creatorcontrib><creatorcontrib>Avdeev, Maxim</creatorcontrib><creatorcontrib>Ling, Chris D</creatorcontrib><creatorcontrib>Kennedy, Brendan J</creatorcontrib><collection>MEDLINE - Academic</collection><jtitle>Inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Wang, Chun-Hai</au><au>Gui, Dong-Yun</au><au>Xia, Qingbo</au><au>Avdeev, Maxim</au><au>Ling, Chris D</au><au>Kennedy, Brendan J</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Structure Evolution of Na2O2 from Room Temperature to 500 °C</atitle><jtitle>Inorganic chemistry</jtitle><addtitle>Inorg. Chem</addtitle><date>2020-10-05</date><risdate>2020</risdate><volume>59</volume><issue>19</issue><spage>14439</spage><epage>14446</epage><pages>14439-14446</pages><issn>0020-1669</issn><eissn>1520-510X</eissn><abstract>Na2O2 is one of the possible discharge products from sodium–air batteries. Here, we report the evolution of the structure of Na2O2 from room temperature to 500 °C using variable-temperature neutron and synchrotron X-ray powder diffraction. A phase transition from α-Na2O2 to β-Na2O2 is observed in the neutron diffraction measurements above 400 °C, and the crystal structure of β-Na2O2 is determined from neutron diffraction data at 500 °C. α-Na2O2 adapts a hexagonal P 62m (no. 189) structure, and β-Na2O2 adapts a tetragonal I41/acd (no. 142) structure. The thermal expansion coefficients of α-Na2O2 are a = 2.98(1) × 10–5 K–1, c = 2.89(1) × 10–5 K–1, and V = 8.96(1) × 10–5 K–1 up to 400 °C, and a ∼10% volume expansion occurs during the phase transition from α-Na2O2 to β-Na2O2 due to the realignment/rotation of O2 2– groups. Both phases are electronic insulators according to DFT calculations with band gaps (both indirect) of 1.75 eV (α-Na2O2) and 2.56 eV (β-Na2O2). An impedance analysis from room temperature to 400 °C revealed a significant enhancement of the conductivity at T ≥ 275 °C. α-Na2O2 shows a higher conductivity (∼10 times at T ≤ 275 °C and ∼3 times at T > 275 °C) in O2 compared to in Ar. We confirmed, by dielectric analysis, that this enhanced conductivity is dominated by ionic conduction.</abstract><pub>American Chemical Society</pub><doi>10.1021/acs.inorgchem.0c02234</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0003-2366-5809</orcidid><orcidid>https://orcid.org/0000-0003-2205-3106</orcidid><orcidid>https://orcid.org/0000-0001-5527-199X</orcidid><orcidid>https://orcid.org/0000-0002-7187-4579</orcidid></addata></record> |
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title | Structure Evolution of Na2O2 from Room Temperature to 500 °C |
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