Solubilities of Ethylene and Carbon Dioxide Gases in Lithium-Ion Battery Electrolyte

Mel Soto; Kae Fink; Christof Zweifel; Peter J. Weddle; Evan Walter Clark Spotte-Smith; Gabriel M. Veith; Kristin A. Persson; Andrew M. Colclasure; Bertrand J. Tremolet de Villers

doi:10.1021/acs.jced.3c00692

Solubilities of Ethylene and Carbon Dioxide Gases in Lithium-Ion Battery Electrolyte

Mel Soto
, Kae Fink
, Christof Zweifel
, Peter J. Weddle
, Evan Walter Clark Spotte-Smith
, Gabriel M. Veith
, Kristin A. Persson
, Andrew M. Colclasure
, Bertrand J. Tremolet de Villers

Energy Storage & Conversion

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

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 Formula Presented 2.0 × 10⁴ kPa for C₂H₄ and k_CO₂ = 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.

Original language	English
Pages (from-to)	2236-2243
Number of pages	8
Journal	Journal of Chemical and Engineering Data
Volume	69
Issue number	6
DOIs	https://doi.org/10.1021/acs.jced.3c00692
State	Published - Jun 13 2024

Funding

This work is authored in part by the National Renewable Energy Laboratory (M.S., K.F., C.Z., P.J.W., A.M.C. and B.T.d.V.), operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy (DOE) under Contract no. DE-AC36-08GO8308. This research was supported by the U.S. Department of Energy’s Vehicle Technologies Office under the Silicon Consortium Project, directed by Brian Cunningham and managed by Anthony Burrell. This work was also supported in part by the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists (WDTS) under the Science Undergraduate Laboratory Internships Program (SULI) (M.S. and C.Z.). Additional support was provided by the Kavli Energy NanoScience Institute Philomathia Graduate Student Fellowship (E.W.C.S.-S.). Data for this study was produced using computational resources provided by the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility under Contract no. DE-AC02-05CH11231, the Eagle HPC system at the National Renewable Energy Laboratory (NREL), and the Lawrencium HPC cluster at Lawrence Berkeley National Laboratory (P.J.W., E.W.C.S.-S., A.M.C., and K.A.P.). A portion of this manuscript has been authored by UT-Battelle, LLC (G.M.V.), under Contract DE-AC05-00OR22725 with the U.S. Department of Energy. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes. 2

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@article{9f92782b0d684f6bb5e1f4da21236b3b,

title = "Solubilities of Ethylene and Carbon Dioxide Gases in Lithium-Ion Battery Electrolyte",

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{\textquoteright}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{\textquoteright}s law constants of Formula Presented 2.0 × 104 kPa for C2H4 and kCO2 = 1.1 × 104 kPa for CO2. These values are compared to Henry{\textquoteright}s law constants predicted from density functional theory and show good agreement within a factor of 3.",

author = "Mel Soto and Kae Fink and Christof Zweifel and Weddle, \{Peter J.\} and Spotte-Smith, \{Evan Walter Clark\} and Veith, \{Gabriel M.\} and Persson, \{Kristin A.\} and Colclasure, \{Andrew M.\} and \{Tremolet de Villers\}, \{Bertrand J.\}",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors. Published by American Chemical Society",

year = "2024",

month = jun,

day = "13",

doi = "10.1021/acs.jced.3c00692",

language = "English",

volume = "69",

pages = "2236--2243",

journal = "Journal of Chemical and Engineering Data",

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T1 - Solubilities of Ethylene and Carbon Dioxide Gases in Lithium-Ion Battery Electrolyte

AU - Soto, Mel

AU - Fink, Kae

AU - Zweifel, Christof

AU - Weddle, Peter J.

AU - Spotte-Smith, Evan Walter Clark

AU - Veith, Gabriel M.

AU - Persson, Kristin A.

AU - Colclasure, Andrew M.

AU - Tremolet de Villers, Bertrand J.

PY - 2024/6/13

Y1 - 2024/6/13

N2 - 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 Formula Presented 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.

AB - 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 Formula Presented 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.

UR - https://www.scopus.com/pages/publications/85193959516

U2 - 10.1021/acs.jced.3c00692

DO - 10.1021/acs.jced.3c00692

M3 - Article

AN - SCOPUS:85193959516

SN - 0021-9568

VL - 69

SP - 2236

EP - 2243

JO - Journal of Chemical and Engineering Data

JF - Journal of Chemical and Engineering Data

IS - 6

ER -

Solubilities of Ethylene and Carbon Dioxide Gases in Lithium-Ion Battery Electrolyte

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