Nimh Gas Model for Dynamic Behaviour Study

Abstract

The NiMH battery is an intercalation battery with a positive NiOH electrode and a negative metal hydride electrode. The electrolyte used is a highly alkaline aqueous solution, typically 6:1 KOH:LiOH. As a consequence of this and the reaction potentials of the electrodes, splitting of water into its constituting elements is a part of normal battery operation. When charging at high SOC, as well as when overcharging, oxygen is formed as a side-reaction. It then diffuses through the separator and recombines at the negative electrode. This recombination cycle causes the temperature in the battery to rise, something that is commonly used to terminate battery charging, either through ΔT or -ΔV criteria. In addition to oxygen production at high state of charge, overdischarging of the battery can produce hydrogen at the positive electrode, with a pressure increase at end of discharge indicating a harmful overdischarge of the battery [1]. Hydrogen is also present in the battery gas composition as a consequence of the negative hydrogen intercalation electrode material which is in equilibrium with gaseous hydrogen, an equilibrium which shifts with electrode hydrogen content [2]. Figure Left: A schematic showing the main gas reactions in the metal NiMH battery. Right: An example cycle of a NiMH battery, showing cell voltage (blue), cell gas pressure (green) and cell surface temperature (teal).The internal gas reactions of the NiMH battery have a great impact on battery function, both in regard to energy efficiency and battery aging. While measurements of battery internal total gas pressure occur in some battery systems, measurements of individual constituents would be impractical in the field, as such measurements require laboratory equipment. Therefore, a gas model that can estimate the internal pressure distribution under dynamic conditions would be a valuable tool to study the effects of different application drive cycles, as well as a possibility to further enhance BMS function for battery stability and longevity.There have been many attempts at modeling the gaseous side reactions in the NiMH battery. Some of these models are part of comprehensive battery models, which combines a voltage response model with added side reactions [3,4]. Other models look only at specific gas related processes [5]. However, a limitation with these models is that they are not able to model the battery during dynamic current conditions. The main reason for this is the presence of a strong open circuit voltage hysteresis, something that these models do not capture well.This study presents a model of the gas reactions and heat generation in the NiMH battery. The model is not coupled to a voltage model, instead it simulates internal temperature and pressure when supplied with experimental current, voltage and surface temperature data. This removes the complication of the open circuit voltage hysteresis effect and lets us model dynamic battery behavior. The model is in zero dimensions and based on physical principles. There are several parameters that are optimized by fitting to experimental data. The model is then validated by simulating pressure for a second set of data, based on the fitted values of the parameters. The simplicity of the model not only allows for it to be used in battery monitoring hardware, it can also be coupled to voltage and multidimensional models to build a more comprehensive predictive model.References Notten, P. H. L.; Latroche, M. Nickel-Metal Hydride: Metal Hydrides. In Encyclopedia of Electrochemical Power Sources; Garche, J., Dyer, C., Moseley, P., Ogumi, Z., Rand, D., Scrosati, B., Eds.; Elsevier B.V., 2009; Vol. 50, pp 502–521.Tserolas, V.; Katagiri, M.; Onodera, H.; Ogawa, H. Thermodynamical Modeling of P-C Isotherms for Metal Hydride Materials. Trans. Mater. Res. Soc. Japan 2010, 35 (2), 221–226. https://doi.org/10.14723/tmrsj.35.221.Albertus, P.; Christensen, J.; Newman, J. Modeling Side Reactions and Nonisothermal Effects in Nickel Metal-Hydride Batteries. J. Electrochem. Soc. 2008, 155 (1), A48. https://doi.org/10.1149/1.2801381.Ledovskikh, A.; Verbitskiy, E.; Ayeb, A.; Notten, P. H. L. Modelling of Rechargeable NiMH Batteries. J. Alloys Compd. 2003, 356–357, 742–745. https://doi.org/10.1016/S0925-8388(03)00082-3.Notten, P. H. L.; Ouwerkerk, M.; Ledovskikh, A.; Senoh, H.; Iwakura, C. Hydride-Forming Electrode Materials Seen from a Kinetic Perspective. J. Alloys Compd. 2003, 356–357, 759–763. https://doi.org/10.1016/S0925-8388(03)00085-9. Figure 1