{"title":"Electrolyte Strategies to Minimize Surface Reactivity for Improved Reversibility of H2 – H3 Phase Transition","authors":"J. Brandon Adamo, Arumugam Manthiram","doi":"10.1039/d4ta05216a","DOIUrl":null,"url":null,"abstract":"High-nickel layered oxide cathodes are promising candidates for application in next-generation lithium-ion batteries. However, they are plagued by high surface reactivity with electrolytes and poor reversibility of the high voltage H2 – H3 phase transition. While electrolytes generally impact cathode surface reactivity, herein we demonstrate that the use of advanced electrolytes can greatly improve the reversibility of the bulk H2 – H3 phase transition due to a reduction in surface reactivity and resultant surface reconstruction. We compare the ability of several common electrolyte enhancement strategies to improve the reversibility of the H2 – H3 phase transition with a LiNiO2 cathode. We find that while all strategies tested in this study improve the reversibility of the phase transition, a combination of fluorinated solvents and an LiPO2F2 additive yields the best results in galvanostatic cycling. We quantitatively measure the capacity loss in the H2 – H3 phase transition region with second derivative analysis and show that the degree of capacity fade is different in different phase transition regions. With galvanostatic intermittent titration technique and galvanostatic electrochemical impedance spectroscopy, we find that advanced electrolytes can reduce the resistance growth with cycling when passing through the H2 – H3 phase transition. With cyclic step chronoamperometry, we examine the evolution of the high-rate performance of the phase transition in each electrolyte and find that a combination of surface stabilization and conductivity are needed to optimize high-rate performance.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":10.7000,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Materials Chemistry A","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1039/d4ta05216a","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}
引用次数: 0
Abstract
High-nickel layered oxide cathodes are promising candidates for application in next-generation lithium-ion batteries. However, they are plagued by high surface reactivity with electrolytes and poor reversibility of the high voltage H2 – H3 phase transition. While electrolytes generally impact cathode surface reactivity, herein we demonstrate that the use of advanced electrolytes can greatly improve the reversibility of the bulk H2 – H3 phase transition due to a reduction in surface reactivity and resultant surface reconstruction. We compare the ability of several common electrolyte enhancement strategies to improve the reversibility of the H2 – H3 phase transition with a LiNiO2 cathode. We find that while all strategies tested in this study improve the reversibility of the phase transition, a combination of fluorinated solvents and an LiPO2F2 additive yields the best results in galvanostatic cycling. We quantitatively measure the capacity loss in the H2 – H3 phase transition region with second derivative analysis and show that the degree of capacity fade is different in different phase transition regions. With galvanostatic intermittent titration technique and galvanostatic electrochemical impedance spectroscopy, we find that advanced electrolytes can reduce the resistance growth with cycling when passing through the H2 – H3 phase transition. With cyclic step chronoamperometry, we examine the evolution of the high-rate performance of the phase transition in each electrolyte and find that a combination of surface stabilization and conductivity are needed to optimize high-rate performance.
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.