Balachandran Radhakrishnan

Thermal Stability and Reactivity of Cathode Materials for Li-Ion Batteries

The thermal stability of electrochemically delithiated Li0.1Ni0.8Co0.15Al0.05O2 (NCA), FePO4 (FP), Mn0.8Fe0.2PO4 (MFP), hydrothermally synthesized VOPO4, LiVOPO4, and electrochemically lithiated Li2VOPO4 is investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis, coupled with mass spectrometry (TGA-MS). The thermal stability of the delithiated materials is found to be in the order of NCA < VOPO4 < MFP < FP. Unlike the layered oxides and MFP, VOPO4 does not evolve O2 on heating. Thus, VOPO4 is less likely to cause a thermal run-away phenomenon in batteries at elevated temperature and so is inherently safer. The lithiated materials LiVOPO4, Li2VOPO4, and LiNi0.8Co0.15Al0.05O2 are found to be stable in the presence of electrolyte, but sealed-capsule high-pressure experiments show a phase transformation of VOPO4 → HVOPO4 → H2VOPO4 when VOPO4 reacts with electrolyte (1 M LiPF6 in EC/DMC = 1:1) between 200 and 300 °C. Using first-principles calculations, we confirm that the charged VOPO4 cathode is indeed predicted to be marginally less stable than FP but significantly more stable than NCA in the absence of electrolyte. An analysis of the reaction equilibria between VOPO4 and EC using a multicomponent phase diagram approach yields products and reaction enthalpies that are highly consistent with the experiment results.

Aqueous Stability of Alkali Superionic Conductors from First-Principles Calculations

Ceramic alkali superionic conductor solid electrolytes (SICEs) play a prominent role in the development of rechargeable alkali-ion batteries, ranging from replacement of organic electrolytes to being used as separators in aqueous batteries. The aqueous stability of SICEs is an important property in determining their applicability in various roles. In this work, we analyze the aqueous stability of twelve well-known Li-ion and Na-ion SICEs using Pourbaix diagrams constructed from first principles calculations. We also introduce a quantitative free energy measure to compare the aqueous stability of SICEs under different environments. Our results show that though oxides are in general more stable in aqueous environments than sulfides and halide-containing chemistries, the cations present play a crucial role in determining whether solid phases are formed within the voltage and pH ranges of interest.

Ab Initio Molecular Dynamics Studies of Fast Ion Conductors

Ab initio molecular dynamics (AIMD) is emerging as a computational technique of choice in the study of the kinetics of materials, especially fast ionic conductors that are of immense interest to energy storage and other application. In this chapter, we will first provide an introduction of the theoretical underpinnings of AIMD, including both the Car-Parrinello and Born-Oppenheimer variants and the analysis of such simulations for diffusion properties. As for defects that are frequently introduced via aliovalent doping and are crucial for tuning the ionic conductivity in the conductors, we will briefly discuss the first principles techniques that allow us to measure the dopability of materials. Finally, we will review several application-driven examples, such as electrolytes for solid oxide fuel cells and rechargeable alkali-ion batteries, wherein AIMD techniques have provided useful insights for materials design.