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This article demonstrates the design of charging strategies for lithium ion batteries with considering the balance between diffusion induced stress and total charge time for two- and three-stage charge methods. For the two-stage galvanostatic-potentiostatic charge method the low mechanical stress can be achieved without increasing total charge time by switching the galvanostatic to the potentiostatic at the time moment when the lithium concentration at the surface of particles reaches the limit c ¯ surf = 0 . A three-stage method, which consists of an initial galvanostatic stage of high current, a galvanostatic stage of low current and a potentiostatic ending stage, is suggested. Employing the initial galvanostatic stage of high current is helpful not only in accelerating the charge process, but also in controlling the mechanical stress once the electrical current and time duration of the initial galvanostatic stage are properly designed. [ABSTRACT FROM AUTHOR]

The state of charge (SOC) or the depth of discharge (DOD) to and the time to delamination onset and the critical size for delamination, which are potentially important in lithium ion battery design for preventing the patterned thin film electrodes from delamination, are investigated. A theoretical approach based on the cohesive model is proposed to formulate the time to and the SOC (or DOD) to delamination onset, as well as the critical size for patterned disk-like electrodes. It is found that for negative electrode the delamination initiation is dominated by mode-II during cell charging and by mode-I during cell discharging. For positive electrode both delamination modes are theoretically possible during cell charging. When the electrochemical load factor i ¯ is very high, the mode-I delamination is possible and an optimal size of electrodes exists for a given maximum i ¯ . The SOC to mode-II delamination onset decreases significantly with increasing dimensionless radius, being independent of i ¯ . When the mode-II is the dominated mode the critical size for delamination exists, and a formula for the critical size for delamination has been deduced, which is proportional to interface ductility and inversely proportional to maximum volumetric strain. [ABSTRACT FROM AUTHOR]

Abstract: In this paper, structural configuration of layered Li-ion battery electrode plates is evaluated by analytically formulating the diffusion induced stress. Both symmetric electrode and asymmetric bilayer electrode are discussed. The thickness ratio and the modulus ratio of current collector to active plate are analytically identified to be the important influence parameters on the stress. Applying a material with smaller elastic modulus for current collector could reduce the peak stresses in both current collector and active plate. Increasing the thickness of current collector would reduce the stress in itself while promote the stress in active plate. Therefore, from mechanical viewpoint on designing an electrode, the material for current collector should be as soft and flexible as possible. And the thickness of current collector should be in an appropriate range. Basically, it should be as small as possible on the precondition that the mechanical strength is satisfied. Finally, effects of three charging conditions, i.e. uniform, galvanostatic, and potentiostatic, on the diffusion induced stress is discussed. It is found the maximum stresses for three cases are linear to the total amount of intercalated lithium ions. Based on the stresses, an optimized charging operation, i.e. first galvanostatic followed by potentiostatic, is suggested. [Copyright &y& Elsevier]

This paper discovers and reveals a phenomenon of feigned death induced by partial delithiation in silicon composite electrodes. Unexpected extremely rapid capacity fading occurs in the initial dozens of the cycles with low upper cut-off voltages. By looking into the irreversibility, the crack, the elemental analysis and the thickness/weight of the electrode, it suggests that the rapid capacity fading is not induced by degradation. Additionally, by providing a reboot with full delithiation, the capacity can be recovered completely, which confirms the integrity of the electrode. This novel type of capacity fading is named by "feigned death" to distinguish it from the "true death" caused by degradation. It is further confirmed that the feigned death is caused by the asymmetric phase transformation between crystalline and amorphous phases in silicon electrodes. When the depth of lithiation is high enough to generate the c-Li 3.75 Si phase but the depth of delithiation is too low to eliminate the generated crystalline phase, the feigned death is triggered. The findings of this work provide an in-depth understanding of the electrochemical performance of Si-based electrodes. • The impact of partial delithiation on cycling performances of silicon electrodes is revealed. • Feigned death of silicon electrodes is discovered. • Feigned death is caused by the asymmetric phase transformation of lithiated silicon. [ABSTRACT FROM AUTHOR]

An analytical model of mechanical contact problems in composite electrodes of lithium-ion batteries is developed in this article. Two typical types of mechanical contact, namely contact between particles and contact between particle and current collector, are investigated. Key parameters that affect the contact problem are identified from the analytical solution. High uniformity of the particle size is found to be critical to the electrode. Furthermore, a soft current collector could significantly reduce the contact stress and hence is also suggested. It is figured out that contact stress is comparable to or even higher than the diffusion-induced stress under free-expansion state, even if the mechanical constraint in electrodes is weak. To highlight the significance of contact stress, an electrochemical cycling verification experiment which involves a charging pause is conducted. Both analytical and experimental results indicate that the mechanical contact plays a crucial role in the evaluation of mechanical stability of lithium-ion battery electrodes. • Analytical solutions of PP and PC contact are established. • The contact stress can be higher than the diffusion-induced stress. • The stress within the active particle is mainly induced by mechanical contacts. [ABSTRACT FROM AUTHOR]

This work focuses on understanding the role of various binders, including sodium alginate (SA), Nafion, and polyvinylidene fluoride (PVDF), on the mechanical behavior and cracking resistance of silicon composite electrodes during electrochemical cycling. In situ curvature measurement of bilayer electrodes, consisting of a silicon-binder-carbon black composite layer on a copper foil, is used to determine the effects of binders on bending deformation, elastic modulus, and stress on the composite electrodes. It is found that the lithiation induced curvature and the modulus of the silicon/SA electrodes are larger than those of electrodes with Nafion and PVDF as binders. Although the modulus of Nafion is smaller than that of PVDF, the curvature and the modulus of silicon/Nafion composite are larger than those of silicon/PVDF electrodes. The moduli of all three composites decrease not only during lithiation but also during delithiation. Based on the measured stress and scanning electron microscopy observations of cracking in the composite electrodes, we conclude that the stress required to crack the composite electrodes with SA and Nafion binders is considerably higher than that of the silicon/PVDF electrode during electrochemical cycling. Thus, the cracking resistance of silicon/SA and silicon/Nafion composite electrodes is higher than that of silicon/PVDF electrodes. [ABSTRACT FROM AUTHOR]

Mechanical properties and lithiation-induced stress are crucial to the performance and durability of lithium-ion batteries. Here, we report the evolution of elastic modulus and stress in a silicon/polyvinylidene fluoride (PVDF) composite electrode coated on a copper foil, along with a model for analyzing the large change in the radius of curvature of the composite electrode/copper foil cantilever. The radius of curvature of the cantilever is captured by a video camera during lithiation/delithiation. The elastic modulus of the composite electrode decreases from about 0.64 GPa to 0.18 GPa during lithiation. It decreases further to about 0.10 GPa after delithiation, which is caused by the fracture of the electrode. The magnitude of the compressive stress increases lineally during lithiation and decreases suddenly to reach a steady state value during delithiation. [ABSTRACT FROM AUTHOR]