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Vías de oxidación de electrolitos en baterías de iones de litio

Bernardine L D Rinkel1, David S Hall1,2, Israel Temprano1

  • 1Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, U.K.

Journal of the American Chemical Society
|July 23, 2020
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La oxidación química, impulsada por la liberación reactiva de oxígeno desde el electrodo positivo, domina la descomposición del electrolito de la batería de iones de litio. Este hallazgo es crucial para mejorar la vida útil y el rendimiento de la batería, especialmente en aplicaciones de alto voltaje.

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Área de la Ciencia:

  • La electroquímica
  • Ciencias de los materiales
  • Tecnología de baterías

Sus antecedentes:

  • La descomposición del electrolito en las baterías de iones de litio limita la vida útil y el rendimiento del dispositivo.
  • La comprensión de los complejos mecanismos de descomposición es un desafío debido a las variadas composiciones y condiciones de funcionamiento.

Objetivo del estudio:

  • Investigar los mecanismos de oxidación y reducción de electrolitos a múltiples tensiones de la célula.
  • Elucidar las vías de descomposición dominantes en las células basadas en LiCoO2.

Principales métodos:

  • Utilizó mediciones de presión *operando*, resonancia magnética nuclear de solución (RMN) y técnicas electroquímicas.
  • Se utilizan celdas LiCoO2/Li de dos compartimentos con un separador de vidrio-cerámica conductor de iones de litio para aislar las reacciones de los electrodos.

Principales resultados:

  • La oxidación química, iniciada por la liberación reactiva de oxígeno de LiCoO2 a altos estados de carga (inicio ~ 4.7 V vs Li / Li +), es el proceso de descomposición primario en el electrodo positivo.
  • Productos de descomposición de electrolitos solubles identificados formados en ambos electrodos.
  • Se estableció un esquema de reacción detallado que racionaliza la formación de especies observadas.

Conclusiones:

  • La descomposición del electrolito en el electrodo positivo está intrínsecamente relacionada con la reactividad superficial del material activo y la liberación de oxígeno.
  • Los hallazgos proporcionan información crítica para mitigar la degradación en materiales de cátodo de LiCoO2 de alto voltaje y que contienen níquel (por ejemplo, NMC).
  • Comprender estos mecanismos es clave para mejorar la longevidad y el rendimiento de las baterías de iones de litio avanzadas.