Mel Soto, Kae Fink, Christof Zweifel, Peter J. Weddle, Evan Walter Clark Spotte-Smith, Gabriel M. Veith, Kristin A. Persson, Andrew M. Colclasure and Bertrand J. Tremolet de Villers*,
{"title":"Solubilities of Ethylene and Carbon Dioxide Gases in Lithium-Ion Battery Electrolyte","authors":"Mel Soto, Kae Fink, Christof Zweifel, Peter J. Weddle, Evan Walter Clark Spotte-Smith, Gabriel M. Veith, Kristin A. Persson, Andrew M. Colclasure and Bertrand J. Tremolet de Villers*, ","doi":"10.1021/acs.jced.3c00692","DOIUrl":null,"url":null,"abstract":"<p >During Li-ion battery operation, (electro)chemical side reactions occur within the cell that can promote or degrade performance. These complex reactions produce byproducts in the solid, liquid, and gas phases. Studying byproducts in these three phases can help optimize battery lifetimes. To relate the measured gas-phase byproducts to species dissolved in the liquid-phase, equilibrium proprieties such as the Henry’s law constants are required. The present work implements a pressure decay experiment to determine the thermodynamic equilibrium concentrations between the gas and liquid phases for ethylene (C<sub>2</sub>H<sub>4</sub>) and carbon dioxide (CO<sub>2</sub>), which are two gases commonly produced in Li-ion batteries, with an electrolyte of 1.2 M LiPF<sub>6</sub> in 3:7 wt/wt ethylene carbonate/ethyl methyl carbonate and 3 wt % fluoroethylene carbonate (15:25:57:3 wt % total composition). The experimentally measured pressure decay curve is fit to an analytical dissolution model and extrapolated to predict the final pressure at equilibrium. The relationship between the partial pressures and concentration of dissolved gas in electrolyte at equilibrium is then used to determine Henry’s law constants of <i></i><math><msub><mi>k</mi><mrow><msub><mi>C</mi><mn>2</mn></msub><msub><mi>H</mi><mn>4</mn></msub></mrow></msub><mo>=</mo></math> 2.0 × 10<sup>4</sup> kPa for C<sub>2</sub>H<sub>4</sub> and <i>k</i><sub>CO<sub>2</sub></sub> = 1.1 × 10<sup>4</sup> kPa for CO<sub>2</sub>. These values are compared to Henry’s law constants predicted from density functional theory and show good agreement within a factor of 3.</p>","PeriodicalId":42,"journal":{"name":"Journal of Chemical & Engineering Data","volume":null,"pages":null},"PeriodicalIF":2.0000,"publicationDate":"2024-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jced.3c00692","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical & Engineering Data","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jced.3c00692","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
During Li-ion battery operation, (electro)chemical side reactions occur within the cell that can promote or degrade performance. These complex reactions produce byproducts in the solid, liquid, and gas phases. Studying byproducts in these three phases can help optimize battery lifetimes. To relate the measured gas-phase byproducts to species dissolved in the liquid-phase, equilibrium proprieties such as the Henry’s law constants are required. The present work implements a pressure decay experiment to determine the thermodynamic equilibrium concentrations between the gas and liquid phases for ethylene (C2H4) and carbon dioxide (CO2), which are two gases commonly produced in Li-ion batteries, with an electrolyte of 1.2 M LiPF6 in 3:7 wt/wt ethylene carbonate/ethyl methyl carbonate and 3 wt % fluoroethylene carbonate (15:25:57:3 wt % total composition). The experimentally measured pressure decay curve is fit to an analytical dissolution model and extrapolated to predict the final pressure at equilibrium. The relationship between the partial pressures and concentration of dissolved gas in electrolyte at equilibrium is then used to determine Henry’s law constants of 2.0 × 104 kPa for C2H4 and kCO2 = 1.1 × 104 kPa for CO2. These values are compared to Henry’s law constants predicted from density functional theory and show good agreement within a factor of 3.
期刊介绍:
The Journal of Chemical & Engineering Data is a monthly journal devoted to the publication of data obtained from both experiment and computation, which are viewed as complementary. It is the only American Chemical Society journal primarily concerned with articles containing data on the phase behavior and the physical, thermodynamic, and transport properties of well-defined materials, including complex mixtures of known compositions. While environmental and biological samples are of interest, their compositions must be known and reproducible. As a result, adsorption on natural product materials does not generally fit within the scope of Journal of Chemical & Engineering Data.