Improved Properties of Li-Ion Battery Electrodes Protected By Al2O3 and ZnO Ultrathin Layers Prepared By Atomic Layer Deposition

Abstract

Surface modification using thin layers grown by atomic layer deposition (ALD) is an effective strategy for performance improvement of Li-ion batteries. Ultrathin Al2O3 layers are the most studied coating material. In our contribution we compare properties of Al2O3 and ZnO ultrathin layers prepared by ALD on lithium-iron-phosphate (LFP) cathodes and Si-graphite anodes.Ultrathin Al2O3 and ZnO films were grown at 100 °C using trimethylaluminum (TMA) and diethylzinc (DEZ) precursors, respectively, with water vapors as reactant. The growth rates of the Al2O3 and ZnO films were about 0.1 nm/cycle on control flat Si substrates. ALD layers thickness in this study ranged from 5 to 20 cycles. A modified deposition recipe utilizing a prolonged precursor dwell time in the reactor chamber for coverage of the highly porous battery electrodes has been utilized. As TMA, DEZ and H2O all have rather high vapor pressures, we assume that significant part of the electrodes were coated.Porous LFP cathodes (NANOMYTE BE-60E, NEI Corp.) with the thickness of 70 μm were used as a substrate. The average particle size of the LFP substrate was ~ 2 μm with the specific surface area of 15 m2/g and active material loading of 7.3 mg/cm2. Experimental capacity C of the LFP electrode is 170 mAh/g in the voltage range 2.5 - 4.1 V using 0.1 charging/discharging c-rate.As an anode material porous silicon-graphite composite electrode sheets NANOMYTE BE-150E (NEI Corp) with the thickness of 65 μm and composition of active material 20% Si and 65 % graphite were used. The nominal capacity C of the silicon-graphite anode is 750mAh/g in the voltage range 0.05 - 1V using 0.05 charging/discharging c-rate.In our contribution we present specific discharge capacity of the electrodes as a function of charging/discharging cycles. For both pristine and Al2O3 protected LFP cathode sheets specific discharge capacity of 160 mAh/g was achieved at the c-rate of 0.2. The specific capacity of the pristine LFP electrode dropped from 160 mAh/g at the c-rate 0.2 to about 90 mAh/g for the c-rate 1, while the electrode protected by 0.5 nm of Al2O3 saturated at 120 mAh/g. Properties of ZnO- protected LFP cathodes are compared to that covered by Al2O3.Electrochemical properties of the silicon-graphite anode were studied using low c-rate of 0.05. During the first cycles the specific capacity is relatively low due to the formation of the solid-electrolyte interface layer at the surface. After several cycles the capacity increased to the nominal value of 750 mAh/g. In our study we compare the charging/discharging capability of the pristine silicon-graphite anode and that of the electrodes covered by 5 -20 ALD cycles of Al2O3 and ZnO films during the first charging/discharging cycles. We discuss the effect of ALD protecting layers on the rate capability of the silicon-graphite anode. Finally, the results of the electrochemical measurements are compared to those obtained by X-ray photoelectron spectroscopy.