Ilia Tertov, François Fauth, Emmanuelle Suard, Thomas Hansen, François Weill, Pierre-Etienne Cabelguen, Christian Masquelier and Laurence Croguennec
{"title":"LiNi0.46Mn1.54O4合成过程中的相平衡:x射线和中子粉末衍射综合研究","authors":"Ilia Tertov, François Fauth, Emmanuelle Suard, Thomas Hansen, François Weill, Pierre-Etienne Cabelguen, Christian Masquelier and Laurence Croguennec","doi":"10.1039/D5TA01514F","DOIUrl":null,"url":null,"abstract":"<p >A combination of synchrotron X-ray powder diffraction (SXRPD) and neutron powder diffraction (NPD) is used to investigate phase equilibrium during the synthesis of LiNi<small><sub>0.46</sub></small>Mn<small><sub>1.54</sub></small>O<small><sub>4</sub></small> (LNMO) powders from a reagent mixture. A Li-deficient disordered LNMO begins to form at <em>T</em> ≈ 460 °C and as the temperature increases, oxygen release triggers the formation of impurity phases. Advanced structural characterization of quenched LNMO samples, along with <em>in situ</em> SXRPD experiments, reveals that a layered oxide impurity crystallizes between 700 °C and 900 °C. At temperatures of 900 °C and above, this impurity phase transforms into a rock-salt type one, while a Li-rich layered oxide impurity also emerges. This leads to the coexistence of three phases at <em>T</em> ≥ 900 °C: LNMO spinel, rock salt, and Li-rich layered oxide. These transformations affect significantly the composition of the targeted LNMO spinel phase, which highlights the challenges in achieving phase purity with the desired stoichiometry in this complex system. The findings provide valuable insights for optimizing the LNMO synthesis so as to prepare high-performance positive electrode materials.</p>","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":" 28","pages":" 22931-22945"},"PeriodicalIF":9.5000,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ta/d5ta01514f?page=search","citationCount":"0","resultStr":"{\"title\":\"Phase equilibrium during the synthesis of LiNi0.46Mn1.54O4: comprehensive X-ray & neutron powder diffraction study†\",\"authors\":\"Ilia Tertov, François Fauth, Emmanuelle Suard, Thomas Hansen, François Weill, Pierre-Etienne Cabelguen, Christian Masquelier and Laurence Croguennec\",\"doi\":\"10.1039/D5TA01514F\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >A combination of synchrotron X-ray powder diffraction (SXRPD) and neutron powder diffraction (NPD) is used to investigate phase equilibrium during the synthesis of LiNi<small><sub>0.46</sub></small>Mn<small><sub>1.54</sub></small>O<small><sub>4</sub></small> (LNMO) powders from a reagent mixture. A Li-deficient disordered LNMO begins to form at <em>T</em> ≈ 460 °C and as the temperature increases, oxygen release triggers the formation of impurity phases. Advanced structural characterization of quenched LNMO samples, along with <em>in situ</em> SXRPD experiments, reveals that a layered oxide impurity crystallizes between 700 °C and 900 °C. At temperatures of 900 °C and above, this impurity phase transforms into a rock-salt type one, while a Li-rich layered oxide impurity also emerges. This leads to the coexistence of three phases at <em>T</em> ≥ 900 °C: LNMO spinel, rock salt, and Li-rich layered oxide. These transformations affect significantly the composition of the targeted LNMO spinel phase, which highlights the challenges in achieving phase purity with the desired stoichiometry in this complex system. The findings provide valuable insights for optimizing the LNMO synthesis so as to prepare high-performance positive electrode materials.</p>\",\"PeriodicalId\":82,\"journal\":{\"name\":\"Journal of Materials Chemistry A\",\"volume\":\" 28\",\"pages\":\" 22931-22945\"},\"PeriodicalIF\":9.5000,\"publicationDate\":\"2025-06-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2025/ta/d5ta01514f?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Materials Chemistry A\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/ta/d5ta01514f\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Materials Chemistry A","FirstCategoryId":"88","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/ta/d5ta01514f","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Phase equilibrium during the synthesis of LiNi0.46Mn1.54O4: comprehensive X-ray & neutron powder diffraction study†
A combination of synchrotron X-ray powder diffraction (SXRPD) and neutron powder diffraction (NPD) is used to investigate phase equilibrium during the synthesis of LiNi0.46Mn1.54O4 (LNMO) powders from a reagent mixture. A Li-deficient disordered LNMO begins to form at T ≈ 460 °C and as the temperature increases, oxygen release triggers the formation of impurity phases. Advanced structural characterization of quenched LNMO samples, along with in situ SXRPD experiments, reveals that a layered oxide impurity crystallizes between 700 °C and 900 °C. At temperatures of 900 °C and above, this impurity phase transforms into a rock-salt type one, while a Li-rich layered oxide impurity also emerges. This leads to the coexistence of three phases at T ≥ 900 °C: LNMO spinel, rock salt, and Li-rich layered oxide. These transformations affect significantly the composition of the targeted LNMO spinel phase, which highlights the challenges in achieving phase purity with the desired stoichiometry in this complex system. The findings provide valuable insights for optimizing the LNMO synthesis so as to prepare high-performance positive electrode materials.
期刊介绍:
The Journal of Materials Chemistry A, B & C covers a wide range of high-quality studies in the field of materials chemistry, with each section focusing on specific applications of the materials studied. Journal of Materials Chemistry A emphasizes applications in energy and sustainability, including topics such as artificial photosynthesis, batteries, and fuel cells. Journal of Materials Chemistry B focuses on applications in biology and medicine, while Journal of Materials Chemistry C covers applications in optical, magnetic, and electronic devices. Example topic areas within the scope of Journal of Materials Chemistry A include catalysis, green/sustainable materials, sensors, and water treatment, among others.