No Arabic abstract
In mathematical models of lithium-ion batteries, the highly heterogeneous porous electrodes are frequently approximated as comprising spherical particles of uniform size, leading to the commonly-used single-particle model (SPM) when transport in the electrolyte is assumed to be fast. Here electrode heterogeneity is modelled by extending this to a distribution of particle sizes. Unimodal and bimodal particle-size distributions (PSD) are considered. For a unimodal PSD, the effect of the spread of the distribution on the cell dynamics is investigated, and choice of effective particle radius when approximating by an SPM assessed. Asymptotic techniques are used to derive a correction to the SPM valid for narrow, but realistic, PSDs. In addition, it is shown that the heterogeneous internal states of all particles (relevant when modelling degradation, for example) can be efficiently computed after-the-fact. For a bimodal PSD, the results are well approximated by a double-particle model (DPM), with one size representing each mode. Results for lithium iron phosphate with a bimodal PSD show that the DPM captures an experimentally-observed double-plateau in the discharge curve, suggesting it is entirely due to bimodality.
We present a porous electrode model for lithium-ion batteries using Butler--Volmer reaction kinetics. We model lithium concentration in both the solid and fluid phase along with solid and liquid electric potential. Through asymptotic reduction, we show that the electric potentials are spatially homogeneous which decouples the problem into a series of time-dependent problems. These problems can be solved on three distinguished time scales, an early time scale where capacitance effects in the electrode dominate, a mid-range time scale where a spatial concentration gradient forms in the electrolyte, and a long-time scale where each of the electrodes saturate and deplete with lithium respectively. The solid-phase concentration profiles are linear functions of time and the electrolyte potential is everywhere zero, which allows the model to be reduced to a system of two uncoupled ordinary differential equations. Analytic and numerical results are compared with full numerical simulations and experimental discharge curves demonstrating excellent agreement.
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.
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.
Present theories of irreversible energy losses and heat generation within Li-ion cells are unsatisfactory because they are not compatible with energy conservation. This work aims to provide a consistent theoretical treatment of energy transport and losses in such devices. An energy conservation law is derived from the Doyle-Fuller-Newman (DFN) model of a Li-ion cell using a rigorous mathematical approach. The resulting law allows irreversible chemical energy losses to be located to seven different regions of the cell, namely: (i) the electrolyte, (ii) the anode particles, (iii) the cathode particles, (iv) the solid parts of the anode (ohmic losses), (v) the solid parts of the cathode (ohmic losses), (vi) the surfaces of the anode particles (polarisation losses), and (vii) the surfaces of the cathode particles (polarisation losses). Numerical solutions to the DFN model are used to validate the conservation law in the cases of a drive cycle and constant current discharges, and to compare the energy losses occurring in different locations. It is indicated how cell design can be improved, for a specified set of operating conditions, by comparing the magnitude of energy losses in the different regions of the cell.
A porous electrode resulting from unregulated Li growth is the major cause of the low Coulombic efficiency and potential safety hazards of rechargeable Li metal batteries. Strategies aiming to achieve large granular Li deposits have been extensively explored; yet, the ideal Li deposits, which consist of large Li particles that are seamlessly packed on the electrode and can be reversibly deposited and stripped, have never been achieved. Here, by controlling the uniaxial stack pressure during battery operation, a dense Li deposition (99.49% electrode density) with an ideal columnar structure has been achieved. Using multi-scale characterization and simulation, we elucidated the critical role of stack pressure on Li nucleation, growth and dissolution processes, and developed innovative strategies to maintain the ideal Li morphology during extended cycling. The precision manipulation of Li deposition and dissolution is a critical step to enable fast charging and low temperature operation for Li metal batteries.