A model for degradation of electrochemical devices based on linear non-equilibrium thermodynamics and its application to lithium ion batteries

作者：Virkar Anil V^*

来源：Journal of Power Sources, 2011, 196(14): 5970-5984.

DOI：10.1016/j.jpowsour.2011.03.005

• Local equilibrium
• Coupled transport
• Electrochemical devices
• Li ion battery
• Degradation

Transport through ionic conducting membranes is examined. An equation describing the chemical potential, mu(s), of electrically neutral species, s, in the membrane is derived in terms of ionic and electronic currents, and ionic and electronic transport resistances. It is shown that the its in the membrane need not be mathematically bounded by the values at the two electrodes (reservoirs) if the ionic and the electronic currents through the membrane are in the same direction. Conditions could develop under which the mu(s) in the membrane may exceed the thermodynamic stability of the membrane even when exposed to stable conditions at the two electrodes. It is shown that during charging, chemical potential of lithium, mu(Li), in the electrolyte of a lithium-ion battery may exceed that corresponding to pure lithium thus causing lithium precipitation and/or reaction with the electrolyte. It is also shown that in a lithium ion battery pack containing several cells, degradation may occur during discharge due to cell imbalance. In unbalanced cells. the SEI layer may form at both the anode/electrolyte and the cathode/electrolyte interfaces. A bi-layer separator comprising an electronic conductor and an electronic insulator is proposed for improved stability of lithium batteries.

• 出版日期2011-7-15