Attaining Full Li‐Ion Storage Capacity in Nearly Defect‐free and Preferential Orientation Grown LiCoPO4 Via ab initio Solvothermal Crystallization Control

IF 24.4 1区 材料科学 Q1 CHEMISTRY, PHYSICAL
Moohyun Woo, Sang‐Wook Park, Jinhyuk Lee, Dong‐Hwa Seo, George P. Demopoulos
{"title":"Attaining Full Li‐Ion Storage Capacity in Nearly Defect‐free and Preferential Orientation Grown LiCoPO4 Via ab initio Solvothermal Crystallization Control","authors":"Moohyun Woo, Sang‐Wook Park, Jinhyuk Lee, Dong‐Hwa Seo, George P. Demopoulos","doi":"10.1002/aenm.202404404","DOIUrl":null,"url":null,"abstract":"Boosting energy density beyond the current status of Li‐ion batteries is actively sought after yet it remains very challenging. One promising pathway toward this goal is the development of defect‐free high‐voltage cathode materials via novel crystal engineered approaches. In response to this demand, the present study focuses on synthesizing LiCoPO<jats:sub>4</jats:sub>, which is a high‐voltage polyanionic compound, into nearly defect‐free structure and preferential orientation grown crystals via solvothermal method using ethylene glycol (EG) as surface energy control medium. Notably, ab initio molecular dynamics simulations and density functional theory calculations elucidate the role of interfacial energy variations induced by EG molecule interaction with particular crystal facets of LiCoPO<jats:sub>4</jats:sub> giving rise to the desired growth direction in comparison with hydrothermal method. In addition to solvent regulated crystal growth, Argon‐annealing alleviates the undesired charge transfer resistance on the crystal surface by eliminating EG residue and further reduces the anti‐site defect concentration, thereby engineering essentially highly ordered crystal structure. The novel LiCoPO<jats:sub>4</jats:sub> crystals are shown to possess nearly theoretical full discharge capacity (163.0 mAh g<jats:sup>−1</jats:sup> and 774.7 Wh kg<jats:sup>−1</jats:sup> at C/10) and superior rate capability (151.6 mAh g<jats:sup>−1</jats:sup> and 716.9 Wh kg<jats:sup>−1</jats:sup> at 1 C), a truly unmatched functionality offering new high‐voltage cathode design possibilities.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"124 1","pages":""},"PeriodicalIF":24.4000,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advanced Energy Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1002/aenm.202404404","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0

Abstract

Boosting energy density beyond the current status of Li‐ion batteries is actively sought after yet it remains very challenging. One promising pathway toward this goal is the development of defect‐free high‐voltage cathode materials via novel crystal engineered approaches. In response to this demand, the present study focuses on synthesizing LiCoPO4, which is a high‐voltage polyanionic compound, into nearly defect‐free structure and preferential orientation grown crystals via solvothermal method using ethylene glycol (EG) as surface energy control medium. Notably, ab initio molecular dynamics simulations and density functional theory calculations elucidate the role of interfacial energy variations induced by EG molecule interaction with particular crystal facets of LiCoPO4 giving rise to the desired growth direction in comparison with hydrothermal method. In addition to solvent regulated crystal growth, Argon‐annealing alleviates the undesired charge transfer resistance on the crystal surface by eliminating EG residue and further reduces the anti‐site defect concentration, thereby engineering essentially highly ordered crystal structure. The novel LiCoPO4 crystals are shown to possess nearly theoretical full discharge capacity (163.0 mAh g−1 and 774.7 Wh kg−1 at C/10) and superior rate capability (151.6 mAh g−1 and 716.9 Wh kg−1 at 1 C), a truly unmatched functionality offering new high‐voltage cathode design possibilities.
通过从头算溶剂热结晶控制在几乎无缺陷和优先取向生长的LiCoPO4中获得完全的锂离子存储容量
提高锂离子电池的能量密度是人们积极追求的目标,但它仍然非常具有挑战性。实现这一目标的一个有希望的途径是通过新的晶体工程方法开发无缺陷的高压阴极材料。针对这一需求,本研究以乙二醇(EG)为表面能控制介质,采用溶剂热法将高电压聚阴离子化合物LiCoPO4合成成几乎无缺陷结构和择优取向的晶体。值得注意的是,与水热法相比,从头算分子动力学模拟和密度泛函理论计算阐明了EG分子与LiCoPO4的特定晶体面相互作用引起的界面能变化对所需生长方向的作用。除了溶剂调节晶体生长外,氩气退火还通过消除EG残留减轻了晶体表面的电荷转移阻力,并进一步降低了反位缺陷浓度,从而设计出本质上高度有序的晶体结构。新型LiCoPO4晶体具有接近理论的完全放电容量(C/10时163.0 mAh g - 1和774.7 Wh kg - 1)和优越的倍率能力(C时151.6 mAh g - 1和716.9 Wh kg - 1),具有真正无与伦比的功能,提供了新的高压阴极设计可能性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
Advanced Energy Materials
Advanced Energy Materials CHEMISTRY, PHYSICAL-ENERGY & FUELS
CiteScore
41.90
自引率
4.00%
发文量
889
审稿时长
1.4 months
期刊介绍: Established in 2011, Advanced Energy Materials is an international, interdisciplinary, English-language journal that focuses on materials used in energy harvesting, conversion, and storage. It is regarded as a top-quality journal alongside Advanced Materials, Advanced Functional Materials, and Small. With a 2022 Impact Factor of 27.8, Advanced Energy Materials is considered a prime source for the best energy-related research. The journal covers a wide range of topics in energy-related research, including organic and inorganic photovoltaics, batteries and supercapacitors, fuel cells, hydrogen generation and storage, thermoelectrics, water splitting and photocatalysis, solar fuels and thermosolar power, magnetocalorics, and piezoelectronics. The readership of Advanced Energy Materials includes materials scientists, chemists, physicists, and engineers in both academia and industry. The journal is indexed in various databases and collections, such as Advanced Technologies & Aerospace Database, FIZ Karlsruhe, INSPEC (IET), Science Citation Index Expanded, Technology Collection, and Web of Science, among others.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信