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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Nishi, Y. Lithium ion secondary batteries; past 10 years and the future. J. Power Sources 100, 101–106 (2001).
Pistoia, G. Batteries for Portable Devices (Elsevier, 2005).
Vincent, C. A. & Scrosati, B. Modern Batteries (Elsevier, 1997).
Barnard, R., Crickmore, G. T., Lee, J. A. & Tye, F. L. The cause of residual capacity in nickel oxyhydroxide electrodes. J. Appl. Electrochem. 10, 61–70 (1980).
Davolio, G. & Soragni, E. The ‘memory effect’ on nickel oxide electrodes: Electrochemical and mechanical aspects. J. Appl. Electrochem. 28, 1313–1319 (1998).
Huggins, R. A. Mechanism of the memory effect in ‘nickel’ electrodes. Solid State Ion. 177, 2643–2646 (2006).
Sato, Y., Takeuchi, S. & Kobayakawa, K. Cause of the memory effect observed in alkaline secondary batteries using nickel electrode. J. Power Sources 93, 20–24 (2001).
Barbarisi, O., Vasca, F. & Glielmo, L. State of charge Kalman filter estimator for automotive batteries. Control Eng. Practice 14, 267–275 (2006).
Hu, Y. & Yurkovich, S. Battery cell state-of-charge estimation using linear parameter varying system techniques. J. Power Sources 198, 338–350 (2012).
Sleigh, A. K., Murray, J. J. & McKinnon, W. R. Memory effects due to phase conversion and hysteresis in Li/Li x MnO2 cells. Electrochim. Acta 36, 1469–1474 (1991).
Padhi, A. K., Najundaswamy, K. S. & Goodenough, J. B. Phospho-olivines as positive-electrode materials for rechargeable lithium batteries. J. Electrochem. Soc. 144, 1188–1194 (1997).
Yamada, A., Chung, S. C. & Hinokuma, K. Optimized LiFePO4 for lithium battery cathodes. J. Electrochem. Soc. 148, A224–A229 (2001).
Ohzuku, T., Ueda, A. & Yamamoto, N. Zero-strain insertion material of Li[Li1/3Ti5/3]O4 for rechargeable lithium cells. J. Electrochem. Soc. 142, 1431–1435 (1995).
Scharner, S., Weppner, W. & Schmid-Beurmann, P. Evidence of two-phase formation upon lithium insertion into the Li1.33Ti1.67O4 spinel. J. Electrochem. Soc. 146, 857–861 (1999).
Jiang, J. & Dahn, J. R. ARC studies of the thermal stability of three different cathode materials: LiCoO2; Li[Ni0.1Co0.8Mn0.1]O2; and LiFePO4, in LiPF6 and LiBoB EC/DEC electrolytes. Electrochem. Commun. 6, 39–43 (2004).
Jiang, J., Chen, J. & Dahn, J. R. Comparison of the reactions between Li7/3Ti5/3O4 or LiC6 and nonaqueous solvents or electrolytes using accelerating rate calorimetry. J. Electrochem. Soc. 151, A2082–A2087 (2004).
Reale, P. et al. A safe, low-cost, and sustainable lithium-ion polymer battery. J. Electrochem. Soc. 151, A2137–A2142 (2004).
Shim, J. & Striebel, K. A. Effect of electrode density on cycle performance and irreversible capacity loss for natural graphite anode in lithium-ion batteries. J. Power Sources 119–121, 934–937 (2003).
Park, G. et al. The study of electrochemical properties and lithium deposition of graphite at low temperature. J. Power Sources 199, 293–299 (2012).
Bergveld, H. J. et al. Encyclopedia of Electrochemical Power Sources: Adaptive State-of-Charge Determination (Elsevier, 2009).
Ng, K. S. et al. Enhanced coulomb counting method for estimating state-of-charge and state-of-health of lithium-ion batteries. Appl. Energy 86, 1506–1511 (2009).
He, H. et al. Online model-based estimation of state-of-charge and open-circuit voltage of lithium-ion batteries in electric vehicles. Energy 39, 310–318 (2012).
Yazami, R. & Reynier, Y. Thermodynamics and crystal structure anomalies in lithium-intercalated graphite. J. Power Sources 153, 312–318 (2006).
Weppner, W. & Huggins, R. A. Determination of the kinetic parameters of mixed-conducting electrodes and application to the system Li3Sb. J. Electrochem. Soc. 124, 1569–1578 (1977).
Striebel, K. et al. The development of low cost LiFePO4-based high power lithium-ion batteries. J. Power Sources 146, 33–38 (2005).
Guo, X. et al. The preparation of LiFePO4/C cathode by a modified carbon-coated method. J. Electrochem. Soc. 156, A787–A790 (2009).
Joachin, H., Kaun, T. D., Zaghib, K. & Prakash, J. Electrochemical and Thermal studies of LiFePO4 cathode in lithium-ion cells. ECS Trans. 6, 11–16 (2008).
Kao, Y. et al. Overpotential-dependent phase transformation pathways in lithium iron phosphate battery electrodes. Chem. Mater. 22, 5845–5855 (2010).
Dreyer, W. et al. The thermodynamic origin of hysteresis in insertion batteries. Nature Mater. 9, 448–453 (2010).
Andersson, A. S. & Thomas, J. O. The source of first-cycle capacity loss in LiFePO4 . J. Power Sources 97–98, 498–502 (2005).
Laffont, L. et al. Study of the LiFePO4/FePO4 two-phase system by High-resolution electron energy loss spectroscopy. Chem. Mater. 18, 5520–5529 (2006).
Ramana, C. V., Mauger, A., Gendron, F., Julien, C. M. & Zaghib, K. Study of the Li-insertion/extraction process in LiFePO4/FePO4 . J. Power Sources 187, 555–564 (2009).
Delmas, C., Maccario, M., Croguennec, L., Le Cras, F. & Weill, F. Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model. Nature Mater. 7, 665–671 (2008).
Dreyer, W., Guhlke, C. & Robert, H. The behavior of a many-particle electrode in a lithium-ion battery. Physica D 240, 1008–1019 (2011).
Malik, R., Zhou, F. & Ceder, G. Kinetics of non-equilibrium lithium incorporation in LiFePO4 . Nature Mater. 10, 587–590 (2011).
Gong, Z. & Yang, Y. Recent advances in the research of polyanion-type cathode materials for Li-ion batteries. Energy Environ. Sci. 4, 3223–3242 (2011).
Novák, P., Scheifele, W., Joho, F. & Haas, O. Electrochemical insertion of magnesium into hydrated vanadium bronzes. J. Electrochem. Soc. 142, 2544–2550 (1995).
Kondo, H. et al. Effects of Mg-substitution in Li(Ni,Co,Al)O2 positive electrode materials on the crystal structure and battery performance. J. Power Sources 174, 1131–1137 (2007).
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.
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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