{"title":"相变限制了钛基离子筛对锂的吸附","authors":"Hsieh Chen","doi":"10.1016/j.mtphys.2024.101508","DOIUrl":null,"url":null,"abstract":"<div><p>Hydrogen titanium oxide (HTO) is a promising material in extracting lithium ions from dilute sources such as geothermal or oil/gas brines. However, experiments show limited Li adsorption in HTO compared to its theoretical maximum capacity, where all H atoms in HTO are replaced by Li that forms lithium titanium oxide (LTO). Here, <em>ab initio</em> molecular dynamics (AIMD) simulations show clear evidence of phase transitions at specific Li adsorption in pure or doped HTO/LTO, which directly predict their experimental maximum capacity. Analysis of thermodynamic properties as well as layered crystal structures show distinct Li-poor to Li-rich phase transitions in the pure, Mo-doped, and Fe-doped HTO/LTO. In addition, it is observed a second phase transition in the Fe-doped HTO/LTO in the Li-poor phases that further constrains Li adsorption. To the best of my knowledge, this is the first study that accurately predict the experimental capacities in ion sieves from first principle. More importantly, this study puts spotlights on phase transitions as an important consideration in molecular engineering developments of functional separation materials, such as the high-performance lithium-ion sieves presented herein.</p></div>","PeriodicalId":18253,"journal":{"name":"Materials Today Physics","volume":"46 ","pages":"Article 101508"},"PeriodicalIF":10.0000,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Phase transitions limit lithium adsorption in titanium-based ion sieves\",\"authors\":\"Hsieh Chen\",\"doi\":\"10.1016/j.mtphys.2024.101508\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Hydrogen titanium oxide (HTO) is a promising material in extracting lithium ions from dilute sources such as geothermal or oil/gas brines. However, experiments show limited Li adsorption in HTO compared to its theoretical maximum capacity, where all H atoms in HTO are replaced by Li that forms lithium titanium oxide (LTO). Here, <em>ab initio</em> molecular dynamics (AIMD) simulations show clear evidence of phase transitions at specific Li adsorption in pure or doped HTO/LTO, which directly predict their experimental maximum capacity. Analysis of thermodynamic properties as well as layered crystal structures show distinct Li-poor to Li-rich phase transitions in the pure, Mo-doped, and Fe-doped HTO/LTO. In addition, it is observed a second phase transition in the Fe-doped HTO/LTO in the Li-poor phases that further constrains Li adsorption. To the best of my knowledge, this is the first study that accurately predict the experimental capacities in ion sieves from first principle. More importantly, this study puts spotlights on phase transitions as an important consideration in molecular engineering developments of functional separation materials, such as the high-performance lithium-ion sieves presented herein.</p></div>\",\"PeriodicalId\":18253,\"journal\":{\"name\":\"Materials Today Physics\",\"volume\":\"46 \",\"pages\":\"Article 101508\"},\"PeriodicalIF\":10.0000,\"publicationDate\":\"2024-07-09\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Materials Today Physics\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2542529324001846\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Materials Today Physics","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2542529324001846","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
氢氧化钛(HTO)是从地热或石油/天然气盐水等稀释源中提取锂离子的一种有前途的材料。然而,实验表明,与 HTO 的理论最大容量相比,HTO 对锂的吸附有限,在理论最大容量下,HTO 中的所有 H 原子都会被锂取代,形成锂氧化钛(LTO)。在此,ab initio 分子动力学(AIMD)模拟显示了纯 HTO/LTO 或掺杂 HTO/LTO 中特定锂吸附时相变的明显证据,这直接预测了它们的实验最大容量。对热力学性质和层状晶体结构的分析表明,在纯的、掺杂钼和掺杂铁的 HTO/LTO 中存在明显的贫锂到富锂的相变。此外,还观察到掺铁 HTO/LTO 在贫锂相中的第二次相变,这进一步限制了锂的吸附。据我所知,这是第一项根据第一原理准确预测离子筛实验容量的研究。更重要的是,这项研究将相变作为功能分离材料(如本文介绍的高性能锂离子筛)分子工程开发中的一个重要考虑因素。
Phase transitions limit lithium adsorption in titanium-based ion sieves
Hydrogen titanium oxide (HTO) is a promising material in extracting lithium ions from dilute sources such as geothermal or oil/gas brines. However, experiments show limited Li adsorption in HTO compared to its theoretical maximum capacity, where all H atoms in HTO are replaced by Li that forms lithium titanium oxide (LTO). Here, ab initio molecular dynamics (AIMD) simulations show clear evidence of phase transitions at specific Li adsorption in pure or doped HTO/LTO, which directly predict their experimental maximum capacity. Analysis of thermodynamic properties as well as layered crystal structures show distinct Li-poor to Li-rich phase transitions in the pure, Mo-doped, and Fe-doped HTO/LTO. In addition, it is observed a second phase transition in the Fe-doped HTO/LTO in the Li-poor phases that further constrains Li adsorption. To the best of my knowledge, this is the first study that accurately predict the experimental capacities in ion sieves from first principle. More importantly, this study puts spotlights on phase transitions as an important consideration in molecular engineering developments of functional separation materials, such as the high-performance lithium-ion sieves presented herein.
期刊介绍:
Materials Today Physics is a multi-disciplinary journal focused on the physics of materials, encompassing both the physical properties and materials synthesis. Operating at the interface of physics and materials science, this journal covers one of the largest and most dynamic fields within physical science. The forefront research in materials physics is driving advancements in new materials, uncovering new physics, and fostering novel applications at an unprecedented pace.