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Transporte por intercambio de electrolitos en baterías: ¿ultra rápido o ultra lento?
Bogdan Dereka1,2,3,4, Nicholas H C Lewis1,2,3,4, Yong Zhang4,5
1James Franck Institute, The University of Chicago, Chicago, Illinois 60637, United States.
Journal of the American Chemical Society
|April 26, 2022
Resumen
La espectroscopia ultra rápida revela que el intercambio de iones y disolventes en los electrolitos de la batería no ocurre dentro de los 100 picosegundos. La dinámica observada se debe a la transferencia de energía, lo que sugiere interacciones iónico-solvente más lentas de lo que se pensaba anteriormente.
Área de la Ciencia:
- La electroquímica
- Ciencias de los materiales
- Química Física
Sus antecedentes:
- Comprender los mecanismos de transporte de iones en los electrolitos de la batería es crucial para el diseño de electrolitos avanzados.
- Los modelos actuales debaten entre la difusión vehicular y la difusión estructural (intercambio de disolventes) para el transporte de iones.
Objetivo del estudio:
- Diferenciar entre el intercambio químico y la dinámica de transferencia de energía en electrolitos de baterías.
- Para determinar la escala de tiempo de las interacciones entre iones y disolventes en varios electrolitos.
Principales métodos:
- Se utilizó una espectroscopia de infrarrojos bidimensional ultrarrápida (2D IR) en isotopólogos de acetonitrilo.
- Electrolitos investigados que contienen sales de Li+, Mg2+, Zn2+, Ca2+ y Ba2+ bis (trifluorometilsulfonil) imida.
- Combinación de IR 2D con simulaciones de dinámica molecular y mediciones de conductividad.
Principales resultados:
- No se observó evidencia de intercambio iónico-solvente dentro de los 100 picosegundos en todos los iones y concentraciones analizados.
- Todas las dinámicas espectrales se atribuyeron a la transferencia de energía intermolecular, no al intercambio de disolventes.
- Se estableció un límite experimental inferior para los tiempos de residencia del disolvente iónico en varios cientos de picosegundos.
Conclusiones:
- Los tiempos de residencia del disolvente iónico son significativamente más largos de lo sugerido anteriormente.
- El transporte de iones puede verse como un continuo de mecanismos vehiculares y estructurales influenciados por la concentración.
- Los movimientos colectivos de electrolitos juegan un papel vital en el transporte de iones a través de varios sistemas de baterías.
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