Memory effect in a lithium-ion battery

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Abstract

Memory effects are well known to users of nickel–cadmium and nickel–metal-hydride batteries. If these batteries are recharged repeatedly after being only partially discharged, they gradually lose usable capacity owing to a reduced working voltage. Lithium-ion batteries, in contrast, are considered to have no memory effect. Here we report a memory effect in LiFePO4—one of the materials used for the positive electrode in Li-ion batteries—that appears already after only one cycle of partial charge and discharge. We characterize this memory effect of LiFePO4 and explain its connection to the particle-by-particle charge/discharge model. This effect is important for most battery uses, as the slight voltage change it causes can lead to substantial miscalculations in estimating the state of charge of batteries.

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Figure 1: Demonstration of a memory effect in LiFePO4 at a SOC of 50%.
Figure 2: The memory effect in LiFePO4 at several SOCs.
Figure 3: Charge and discharge curve of LiFePO4 and Li4Ti5O12 under memory-effect conditions at SOCs of 30 and 50%.
Figure 4: GITT and constant-current measurements of LiFePO4 and Li4Ti5O12 between 2.4 and 4.4 V versus Li/Li+ for LiFePO4 and 1.0 and 2.1 V for Li4Ti5O12, respectively.
Figure 5: Schematic diagram of the chemical-potential condition of many particles of LiFePO4 during GITT measurement, the memory-writing cycle and the memory-releasing cycle.

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Acknowledgements

We would like to thank C. Villevieille for experimental support and advice, M. Heß for helpful discussions and comments, S. Urbonaite for valuable suggestions on the manuscript and H. Kaiser and C. Junker for all-round technical assistance.

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T.S. conceived and carried out the experiments, analysed the data and wrote the paper, Y.U. directed this work, and P.N. discussed and directed this work.

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Correspondence to Tsuyoshi Sasaki or Petr Novák.

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The authors declare no competing financial interests.

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Sasaki, T., Ukyo, Y. & Novák, P. Memory effect in a lithium-ion battery. Nature Mater 12, 569–575 (2013). https://doi.org/10.1038/nmat3623

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