Sergiy Kalnaus

Investigating phase transformation in the Li1.2Co0.1Mn0.55Ni0.15O2 lithium-ion battery cathode during high-voltage hold (4.5 V) via magnetic, X-ray diffraction and electron microscopy studies

This study is the first that provides evidence of phase transformation in a Li-rich Li1.2Co0.1Mn0.55Ni0.15O2 cathode material for lithium-ion batteries (LIBs) during constant voltage charging. Diffraction and magnetic measurement techniques were successfully implemented to investigate the structural transformation in this cathode material during holding a half-cell at 4.5 V in a charged state. The results from X-ray diffraction showed a decrease in c-lattice parameters during high-voltage hold. Magnetic data revealed an increase in average effective magnetic moments of transition metal (TM) ions at constant voltage corresponding to a change in electronic states of TM ions. Analysis showed the reduction of Ni4+ to Ni2+, which was attributed to charge compensation due to oxygen loss. The appearance of the strong {100} forbidden reflection in the single-crystal selected area electron diffraction (SAED) data was attributed to migration of transition metal ions to the octahedral vacancy sites in the lithium layer during high-voltage hold, which was in agreement with the magnetization results. After prolonged hold at 4.5 V, high-resolution transmission electron microscopy (TEM) images along with SAED results showed the presence of spinel phases in the particles, indicating a layered to spinel like phase transformation at constant voltage in agreement with the magnetic data. The results obtained from these magnetic and diffraction studies furnish the fundamental understanding of the structural transformation pathways in Li-rich cathodes at constant voltage and will be instrumental for modifying the parent structure to achieve greater stability.

Direct Mapping of Ion Diffusion Times on LiCoO2 Surfaces with Nanometer Resolution

The strong coupling between the molar volume and mobile ion concentration in ionically-conductive solids is used for spatially-resolved studies of ionic transport on the polycrystalline LiCoO2 surface by time-resolved spectroscopy. Strong variability between ionic transport at the grain boundaries and within the grains is observed, and the relationship between relaxation and hysteresis loop formation is established. The use of the strain measurements allows ionic transport be probed on the nanoscale, and suggests enormous potential for probing ionic materials and devices.

Structural transformation in a Li1.2Co0.1Mn0.55Ni0.15O2 lithium-ion battery cathode during high-voltage hold

A decrease in the c-lattice parameter was observed in Li1.2Co0.1Mn0.55Ni0.15O2 during constant voltage holding at 4.5 V by in situ X-ray diffraction. Comparison of magnetic susceptibility data before and after high-voltage hold reveals the change in average oxidation states of transition metal ions during high-voltage holding process. Transmission electron microscopy studies show the spinel reflections with fundamental trigonal spots from the particles after high-voltage hold indicating substantial structural modification. The structural transformation was believed to occur due to the oxygen release and/or the migration of transition metal cations to lithium layer during constant voltage holding.

Local Detection of Activation Energy for Ionic Transport in Lithium Cobalt Oxide

Local activation energy for ionic diffusion is probed on the nanometer level in LiCoO(2) thin films using variable temperature electrochemical strain microscopy (ESM). The high spatial resolution of ESM allows one to extract information about ionic activation energies on the level of individual grains and grain facets, thus bridging the lengths scales of atomistic calculations and traditional macroscopic experiments. A series of control experiments have been performed and possible signal generating mechanisms are discussed to explain the temperature-dependent ESM measurements.

Three-dimensional vector electrochemical strain microscopy

Three-dimensional vector imaging of bias-induced displacements of surfaces of ionically conductive materials using electrochemical strain microscopy (ESM) is demonstrated for model polycrystalline LiCoO2surface. We demonstrate that resonance enhanced imaging using band excitation detection can be performed both for out-of-plane and in-plane response components at flexural and torsional resonances of the cantilever, respectively. The image formation mechanism in vector ESM is analyzed and relationship between measured signal and grain orientation is discussed.

Understanding limiting factors in thick electrode performance as applied to high energy density Li-ion batteries

Increasing electrode thickness, thus increasing the volume ratio of active materials, is one effective method to enable the development of high energy density Li-ion batteries. In this study, an energy density versus power density optimization of LiNi0.8Co0.15Al0.05O2 (NCA)/graphite cell stack was conducted via mathematical modeling. The energy density was found to have a maximum point versus electrode thickness (critical thickness) at given discharging C rates. The physics-based factors that limit the energy/power density of thick electrodes were found to be increased cell polarization and underutilization of active materials. The latter is affected by Li-ion diffusion in active materials and Li-ion depletion in the electrolyte phase. Based on those findings, possible approaches were derived to surmount the limiting factors. The improvement of the energy–power relationship in an 18,650 cell was used to demonstrate how to optimize the thick electrode parameters in cell engineering.Graphical Abstract

Multiscale modeling and characterization for performance and safety of lithium-ion batteries

Lithium-ion batteries are highly complex electrochemical systems whose performance and safety are governed by coupled nonlinear electrochemical-electrical-thermal-mechanical processes over a range of spatiotemporal scales. Gaining an understanding of the role of these processes as well as development of predictive capabilities for design of better performing batteries requires synergy between theory, modeling, and simulation, and fundamental experimental work to support the models. This paper presents the overview of the work performed by the authors aligned with both experimental and computational efforts. In this paper, we describe a new, open source computational environment for battery simulations with an initial focus on lithium-ion systems but designed to support a variety of model types and formulations. This system has been used to create a three-dimensional cell and battery pack models that explicitly simulate all the battery components (current collectors, electrodes, and separator). The models are used to predict battery performance under normal operations and to study thermal and mechanical safety aspects under adverse conditions. This paper also provides an overview of the experimental techniques to obtain crucial validation data to benchmark the simulations at various scales for performance as well as abuse. We detail some initial validation using characterization experiments such as infrared and neutron imaging and micro-Raman mapping. In addition, we identify opportunities for future integration of theory, modeling, and experiments.

Safer Batteries through Coupled Multiscale Modeling

Abstract Batteries are highly complex electrochemical systems, with performance and safety governed by coupled nonlinear electrochemical-electrical-thermal-mechanical processes over a range of spatiotemporal scales. We describe a new, open source computational environment for battery simulation known as VIBE - the Virtual Integrated Battery Environment. VIBE includes homogenized and pseudo-2D electrochemistry models such as those by Newman-Tiedemann-Gu (NTG) and Doyle-Fuller-Newman (DFN, a.k.a. DualFoil) as well as a new advanced capability known as AMPERES (Advanced MultiPhysics for Electrochemical and Renewable Energy Storage). AMPERES provides a 3D model for electrochemistry and full coupling with 3D electrical and thermal models on the same grid. VIBE/AMPERES has been used to create three-dimensional battery cell and pack models that explicitly simulate all the battery components (current collectors, electrodes, and separator). The models are used to predict battery performance under normal operations and to study thermal and mechanical response under adverse conditions.

CAEBAT OAS/VIBE Production Release v1.1

The objective of the project is to develop a mathematical and computational infrastructure, and modeling framework that will enable seamless multi-scale and multi-physics simulations of battery performance and safety. The modeling framework will transfer the information between models in a physically consistent and mathematically rigorous fashion for both spatial and temporal variations. The end result will be a verified, computationally scalable, portable, and flexible (extensible and easily-modified) framework that can integrate models from the other CAEBAT tasks and industrial partners. The framework will be used to validate models and modeling approaches against experiments and to support rapid prototyping of advanced battery concepts. Fig. 2 shows different parts of CAEBAT VIBE simulation environment that work together to provide user with flexibility in the problem setup, solution formulation and simulation launch. Each of the parts is discussed in subsequent sections with corresponding examples.