Realistic Ion Dynamics through Charge Renormalization in Nonaqueous ElectrolytesClick to copy article linkArticle link copied!
- Zhixia LiZhixia LiJoint Center for Energy Storage Research, Argonne National Laboratory, Lemont, Illinois 60439, United StatesDepartment of Nuclear, Plasma, and Radiological Engineering, University of Illinois at Urbana−Champaign, Urbana, Illinois61801, United StatesBeckman Institute for Advanced Science and Technology, University of Illinois at Urbana−Champaign, Urbana, Illinois61801, United StatesMore by Zhixia Li
- Lily A. RobertsonLily A. RobertsonJoint Center for Energy Storage Research, Argonne National Laboratory, Lemont, Illinois 60439, United StatesDepartment of Chemistry, University of Illinois at Urbana−Champaign, Urbana, Illinois61801, United StatesChemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois60439, United StatesMore by Lily A. Robertson
- Ilya A. Shkrob*Ilya A. Shkrob*Email: [email protected]Joint Center for Energy Storage Research, Argonne National Laboratory, Lemont, Illinois 60439, United StatesChemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois60439, United StatesMore by Ilya A. Shkrob
- Kyle C. SmithKyle C. SmithBeckman Institute for Advanced Science and Technology, University of Illinois at Urbana−Champaign, Urbana, Illinois61801, United StatesDepartment of Mechanical Science and Engineering, University of Illinois at Urbana−Champaign, Urbana, Illinois61801, United StatesDepartment of Materials Science and Engineering, University of Illinois at Urbana−Champaign, Urbana, Illinois61801, United StatesProgram of Computational Science and Engineering, University of Illinois at Urbana−Champaign, Urbana, Illinois61801, United StatesMore by Kyle C. Smith
- Lei ChengLei ChengJoint Center for Energy Storage Research, Argonne National Laboratory, Lemont, Illinois 60439, United StatesMaterials Science Division, Argonne National Laboratory, Lemont, Illinois60439, United StatesMore by Lei Cheng
- Lu ZhangLu ZhangJoint Center for Energy Storage Research, Argonne National Laboratory, Lemont, Illinois 60439, United StatesChemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois60439, United StatesMore by Lu Zhang
- Jeffrey S. MooreJeffrey S. MooreJoint Center for Energy Storage Research, Argonne National Laboratory, Lemont, Illinois 60439, United StatesBeckman Institute for Advanced Science and Technology, University of Illinois at Urbana−Champaign, Urbana, Illinois61801, United StatesDepartment of Chemistry, University of Illinois at Urbana−Champaign, Urbana, Illinois61801, United StatesDepartment of Materials Science and Engineering, University of Illinois at Urbana−Champaign, Urbana, Illinois61801, United StatesMore by Jeffrey S. Moore
- Y Z*Y Z*Email: [email protected]Joint Center for Energy Storage Research, Argonne National Laboratory, Lemont, Illinois 60439, United StatesDepartment of Nuclear, Plasma, and Radiological Engineering, University of Illinois at Urbana−Champaign, Urbana, Illinois61801, United StatesBeckman Institute for Advanced Science and Technology, University of Illinois at Urbana−Champaign, Urbana, Illinois61801, United StatesProgram of Computational Science and Engineering, University of Illinois at Urbana−Champaign, Urbana, Illinois61801, United StatesDepartment of Electrical and Computer Engineering, University of Illinois at Urbana−Champaign, Urbana, Illinois61801, United StatesMore by Y Z
Abstract
While many practically important electrolytes contain lithium ions, interactions of these ions are particularly difficult to probe experimentally because of their small X-ray and neutron scattering cross sections and large neutron absorption cross sections. Molecular dynamics (MD) is a powerful tool for understanding the properties of nonaqueous electrolyte solutions from the atomic level, but the accuracy of this computational method crucially depends on the physics built into the classical force field. Here, we demonstrate that several force fields for lithium bistriflimide (LiTFSI) in acetonitrile yield a solution structure that is consistent with the neutron scattering experiments, yet these models produce dramatically different ion dynamics in solution. Such glaring discrepancies indicate that inadequate representation of long-range interactions leads to excessive ionic association and ion-pair clustering. We show that reasonable agreement with the experimental observations can be achieved by renormalization of the ion charges using a “titration” method suggested herewith. This simple modification produces realistic concentration dependencies for ionic diffusion and conductivity in <2 M solutions, without loss in quality for simulation of the structure.
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