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Register a new userPhysical modelling of the slow voltage relaxation phenomenon in lithium-ion batteries
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In the lithium-ion battery literature, discharges followed by a relaxation to equilibrium are frequently used to validate models and their parametrizations. Good agreement with experiment during discharge is easily attained with a pseudo-two-dimensional model such as the Doyle-Fuller-Newman (DFN) model. The relaxation portion, however, is typically not well-reproduced, with the relaxation in experiments occurring much more slowly than in models. In this study, using a model that includes a size distribution of the active material particles, we give a physical explanation for the slow relaxation phenomenon. This model, the Many-Particle-DFN (MP-DFN), is compared against discharge and relaxation data from the literature, and optimal fits of the size distribution parameters (mean and variance), as well as solid-state diffusivities, are found using numerical optimization. The voltage after relaxation is captured by careful choice of the current cut-off time, allowing a single set of physical parameters to be used for all C-rates, in contrast to previous studies. We find that the MP-DFN can accurately reproduce the slow relaxation, across a range of C-rates, whereas the DFN cannot. Size distributions allow for greater internal heterogeneities, giving a natural origin of slower relaxation timescales that may be relevant in other, as yet explained, battery behavior.
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A thick electrode with high areal capacity has been developed as a strategy for high-energy-density lithium-ion batteries, but thick electrodes have difficulties in manufacturing and limitations in ion transport. Here, we reported a new manufacturing approach for ultra-thick electrode with aligned structure, called structure electrode additive manufacturing or SEAM, which aligns active materials to the through-thicknesses direction of electrodes using shear flow and a designed printing path. The ultra-thick electrodes with high loading of active materials, low tortuous structure, and good structure stability resulting from a simple and scalable SEAM lead to rapid ion transport and fast electrolyte infusion, delivering a higher areal capacity than slurry-casted thick electrodes. SEAM shows strengths in design flexibility and scalability, which allows the production of practical high energy/power density structure electrodes.
The existence of passivating layers at the interfaces is a major factor enabling modern lithium-ion (Li-ion) batteries. Their properties determine the cycle life, performance, and safety of batteries. A special case is the solid electrolyte interphase (SEI), a heterogeneous multi-component film formed due to the instability and subsequent decomposition of the electrolyte at the surface of the anode. The SEI acts as a passivating layer that hinders further electrolyte disintegration, which is detrimental to the Coulombic efficiency. In this work, we use first-principles simulations to investigate the kinetic and electronic properties of the interface between lithium fluoride (LiF) and lithium carbonate (Li$_2$CO$_3$), two common SEI components present in Li-ion batteries with organic liquid electrolytes. We find a coherent interface between these components that restricts the strain in each of them to below 3%. We find that the interface causes a large increase in the formation energy of the Frenkel defect, generating Li vacancies in LiF and Li interstitials in Li$_2$CO$_3$ responsible for transport. On the other hand, the Li interstitial hopping barrier is reduced from $0.3$ eV in bulk Li$_2$CO$_3$ to $0.10$ or $0.22$ eV in the interfacial structure considered, demonstrating the favorable role of the interface. Controlling these two effects in a heterogeneous SEI is crucial for maintaining fast ion transport in the SEI. We further perform Car-Parrinello molecular dynamics simulations to explore Li ion conduction in our interfacial structure, which reveal an enhanced Li ion diffusion in the vicinity of the interface. Understanding the interfacial properties of the multiphase SEI represents an important frontier to enable next-generation batteries.
Electrolyte stability against oxidation is one of the important factors limiting the development of high energy density batteries. HOMO level of solvent molecules has been successfully used for understanding trends in their oxidative stability but assumes a non-interacting environment. However, solvent HOMO levels are renormalized due to molecules in their solvation shells. In this work, we first demonstrate an inexpensive and accurate method to determine the HOMO level of solvent followed by simple descriptors for renormalization of HOMO level due to different electrolyte components. The descriptors are based on Gutmann Donor and Acceptor numbers of solvent and other components. The method uses fast GGA-level DFT calculations compared to previously used expensive, experimental data dependent methods. This method can be used to screen for unexplored stable solvents among the large number of known organic compounds to design novel high voltage stable electrolytes.
In this article, we derive and discuss a physics-based model for impedance spectroscopy of lithium batteries. Our model for electrochemical cells with planar electrodes takes into account the solid-electrolyte interphase (SEI) as porous surface film. We present two improvements over standard impedance models. Firstly, our model is based on a consistent description of lithium transport through electrolyte and SEI. We use well-defined transport parameters, e.g., transference numbers, and consider convection of the center-of-mass. Secondly, we solve our model equations analytically and state the full transport parameter dependence of the impedance signals. Our consistent model results in an analytic expression for the cell impedance including bulk and surface processes. The impedance signals due to concentration polarizations highlight the importance of electrolyte convection in concentrated electrolytes. We simplify our expression for the complex impedance and compare it to common equivalent circuit models. Such simplified models are good approximations in concise parameter ranges. Finally, we compare our model with experiments of lithium metal electrodes and find large transference numbers for lithium ions. This analysis reveals that lithium-ion transport through the SEI has solid electrolyte character.
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