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The thermodynamic origin of hysteresis in insertion batteries


Lithium batteries are considered the key storage devices for most emerging green technologies such as wind and solar technologies or hybrid and plug-in electric vehicles. Despite the tremendous recent advances in battery research, surprisingly, several fundamental issues of increasing practical importance have not been adequately tackled. One such issue concerns the energy efficiency. Generally, charging of 1010–1017 electrode particles constituting a modern battery electrode proceeds at (much) higher voltages than discharging. Most importantly, the hysteresis between the charge and discharge voltage seems not to disappear as the charging/discharging current vanishes. Herein we present, for the first time, a general explanation of the occurrence of inherent hysteretic behaviour in insertion storage systems containing multiple particles. In a broader sense, the model also predicts the existence of apparent equilibria in battery electrodes, the sequential particle-by-particle charging/discharging mechanism and the disappearance of two-phase behaviour at special experimental conditions.

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Figure 1: Demonstration of the existence of a voltage gap at zero current for three different insertion battery materials.
Figure 2: Precise experiments showing the existence of a zero-current voltage gap in LiFePO4.
Figure 3: Comparison of chemical potential profiles in a single-particle and in a 10-particle system.
Figure 4: Two possible scenarios of new phase formation in a many-particle system.
Figure 5: Interpretation of voltage hysteresis in many-particle insertion systems with fast Li exchange between the particles and a non-monotone single-particle chemical potential.


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The main idea for this work was developed within the former ALISTORE Network of Excellence (now ALISTORE-ERI). The work has been partly supported by the Slovenian Research Agency (Grant No. P2-0148). Another part of the work was carried out as part of Project C26 ‘Storage of Hydrogen in Hydrides’ of the DFG research centre MATHEON, Berlin.

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Correspondence to Miran Gaberšček.

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Dreyer, W., Jamnik, J., Guhlke, C. et al. The thermodynamic origin of hysteresis in insertion batteries. Nature Mater 9, 448–453 (2010).

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