Miao Liu , Xinyue Li , Kun Song , Hang Su , Rucheng Wang , Liwen Hu , Xuewei Lv , Yuntao Xin
{"title":"有前途的正极材料NaV6O15的热力学数据及其合成/分解热力学分析","authors":"Miao Liu , Xinyue Li , Kun Song , Hang Su , Rucheng Wang , Liwen Hu , Xuewei Lv , Yuntao Xin","doi":"10.1016/j.calphad.2023.102645","DOIUrl":null,"url":null,"abstract":"<div><p><span>Sodium-ion batteries have emerged as a promising alternative to lithium-ion batteries due to their lower cost and similar electrochemical properties. The development of high-capacity and long-life electrode materials is crucial for advancing sodium-ion battery research. A significant amount of research has been conducted on the electrochemical properties of NaV</span><sub>6</sub>O<sub>15</sub>, however, there remains a dearth of data on its thermodynamic properties. Herein, NaV<sub>6</sub>O<sub>15</sub> was synthesized using the solid-phase sintering method and thoroughly characterized. Thermodynamic data in the temperature ranges of 298.15–900 K, 15–303 K, and 573–873 K were determined using the Neumann-Kopp rule, low-temperature physical property measurement system, and MHTC 96 line, respectively. The heat capacity equation of NaV<sub>6</sub>O<sub>15</sub> was derived and its enthalpy, entropy, and Gibbs free energy (298.15–800 K) were calculated. Moreover, the thermodynamics of NaV<sub>6</sub>O<sub>15</sub><span>-related formation and decomposition reactions were analyzed. The obtained heat capacity equation of NaV</span><sub>6</sub>O<sub>15</sub> was <span><math><mrow><msub><mi>C</mi><mi>p</mi></msub><mrow><mo>=</mo><mn>517.05524</mn><mo>+</mo><mn>0.08612</mn></mrow><mi>T</mi><mrow><mo>−</mo><mn>1.25053</mn><mo>×</mo><mn>1</mn></mrow><msup><mn>0</mn><mn>7</mn></msup><msup><mi>T</mi><mrow><mo>−</mo><mn>2</mn></mrow></msup><mrow><mo>(</mo><mrow><mi>J</mi><mo>/</mo><mrow><mi>m</mi><mi>o</mi><mi>l</mi><mo>·</mo><mi>K</mi></mrow></mrow><mo>)</mo></mrow><mrow><mo>(</mo><mrow><mn>298.15</mn><mo>∼</mo><mn>873</mn><mi>K</mi></mrow><mo>)</mo></mrow></mrow></math></span>. This study addresses the thermodynamic knowledge gaps of NaV<sub>6</sub>O<sub>15</sub> and provides valuable insights for its preparation and decomposition in manufacturing processes.</p></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":null,"pages":null},"PeriodicalIF":1.9000,"publicationDate":"2023-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Thermodynamic data of a promising cathode material NaV6O15 and its synthesis/decomposition thermodynamic analysis\",\"authors\":\"Miao Liu , Xinyue Li , Kun Song , Hang Su , Rucheng Wang , Liwen Hu , Xuewei Lv , Yuntao Xin\",\"doi\":\"10.1016/j.calphad.2023.102645\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p><span>Sodium-ion batteries have emerged as a promising alternative to lithium-ion batteries due to their lower cost and similar electrochemical properties. The development of high-capacity and long-life electrode materials is crucial for advancing sodium-ion battery research. A significant amount of research has been conducted on the electrochemical properties of NaV</span><sub>6</sub>O<sub>15</sub>, however, there remains a dearth of data on its thermodynamic properties. Herein, NaV<sub>6</sub>O<sub>15</sub> was synthesized using the solid-phase sintering method and thoroughly characterized. Thermodynamic data in the temperature ranges of 298.15–900 K, 15–303 K, and 573–873 K were determined using the Neumann-Kopp rule, low-temperature physical property measurement system, and MHTC 96 line, respectively. The heat capacity equation of NaV<sub>6</sub>O<sub>15</sub> was derived and its enthalpy, entropy, and Gibbs free energy (298.15–800 K) were calculated. Moreover, the thermodynamics of NaV<sub>6</sub>O<sub>15</sub><span>-related formation and decomposition reactions were analyzed. The obtained heat capacity equation of NaV</span><sub>6</sub>O<sub>15</sub> was <span><math><mrow><msub><mi>C</mi><mi>p</mi></msub><mrow><mo>=</mo><mn>517.05524</mn><mo>+</mo><mn>0.08612</mn></mrow><mi>T</mi><mrow><mo>−</mo><mn>1.25053</mn><mo>×</mo><mn>1</mn></mrow><msup><mn>0</mn><mn>7</mn></msup><msup><mi>T</mi><mrow><mo>−</mo><mn>2</mn></mrow></msup><mrow><mo>(</mo><mrow><mi>J</mi><mo>/</mo><mrow><mi>m</mi><mi>o</mi><mi>l</mi><mo>·</mo><mi>K</mi></mrow></mrow><mo>)</mo></mrow><mrow><mo>(</mo><mrow><mn>298.15</mn><mo>∼</mo><mn>873</mn><mi>K</mi></mrow><mo>)</mo></mrow></mrow></math></span>. This study addresses the thermodynamic knowledge gaps of NaV<sub>6</sub>O<sub>15</sub> and provides valuable insights for its preparation and decomposition in manufacturing processes.</p></div>\",\"PeriodicalId\":9436,\"journal\":{\"name\":\"Calphad-computer Coupling of Phase Diagrams and Thermochemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.9000,\"publicationDate\":\"2023-11-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Calphad-computer Coupling of Phase Diagrams and Thermochemistry\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0364591623001177\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0364591623001177","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Thermodynamic data of a promising cathode material NaV6O15 and its synthesis/decomposition thermodynamic analysis
Sodium-ion batteries have emerged as a promising alternative to lithium-ion batteries due to their lower cost and similar electrochemical properties. The development of high-capacity and long-life electrode materials is crucial for advancing sodium-ion battery research. A significant amount of research has been conducted on the electrochemical properties of NaV6O15, however, there remains a dearth of data on its thermodynamic properties. Herein, NaV6O15 was synthesized using the solid-phase sintering method and thoroughly characterized. Thermodynamic data in the temperature ranges of 298.15–900 K, 15–303 K, and 573–873 K were determined using the Neumann-Kopp rule, low-temperature physical property measurement system, and MHTC 96 line, respectively. The heat capacity equation of NaV6O15 was derived and its enthalpy, entropy, and Gibbs free energy (298.15–800 K) were calculated. Moreover, the thermodynamics of NaV6O15-related formation and decomposition reactions were analyzed. The obtained heat capacity equation of NaV6O15 was . This study addresses the thermodynamic knowledge gaps of NaV6O15 and provides valuable insights for its preparation and decomposition in manufacturing processes.
期刊介绍:
The design of industrial processes requires reliable thermodynamic data. CALPHAD (Computer Coupling of Phase Diagrams and Thermochemistry) aims to promote computational thermodynamics through development of models to represent thermodynamic properties for various phases which permit prediction of properties of multicomponent systems from those of binary and ternary subsystems, critical assessment of data and their incorporation into self-consistent databases, development of software to optimize and derive thermodynamic parameters and the development and use of databanks for calculations to improve understanding of various industrial and technological processes. This work is disseminated through the CALPHAD journal and its annual conference.