No Arabic abstract
Using a new class of (BH4)- substituted argyrodite Li6PS5Z0.83(BH4)0.17, (Z = Cl, I) solid electrolyte, Li-metal solid-state batteries operating at room temperature have been developed. The cells were made by combining the modified argyrodite with an In-Li anode and two types of cathode: an oxide, LixMO2 (M = 1/3Ni, 1/3Mn, 1/3Co; so called NMC) and a titanium disulfide, TiS2. The performance of the cells was evaluated through galvanostatic cycling and Alternating Current AC electrochemical impedance measurements. Reversible capacities were observed for both cathodes for at least tens of cycles. However, the high-voltage oxide cathode cell shows lower reversible capacity and larger fading upon cycling than the sulfide one. The AC impedance measurements revealed an increasing interfacial resistance at the cathode side for the oxide cathode inducing the capacity fading. This resistance was attributed to the intrinsic poor conductivity of NMC and interfacial reactions between the oxide material and the argyrodite electrolyte. On the contrary, the low interfacial resistance of the TiS2 cell during cycling evidences a better chemical compatibility between this active material and substituted argyrodites, allowing full cycling of the cathode material, 240 mAhg-1, for at least 35 cycles with a coulombic efficiency above 97%.
Interfacial deposition stability between Li metal and a solid electrolyte (SE) is important in preventing interfacial contact loss, mechanical fracture, and dendrite growth in Li-metal solid-state batteries (SSB). In this work, we investigate the deposition and mechanical stability at the Li metal/SE interface and its consequences (such as SE fracture and contact loss). A wide range of contributing factors are investigated, such as charge and mass transfer kinetics, the plasticity of Li metal and fracture of the SE, and the applied stack pressure. We quantify the effect of the ionic conductivity of the SE, the exchange current density of the interfacial charge-transfer reaction and SE surface roughness on the Li deposition stability at the Li metal/SE interface. We also propose a mechanical stability window for the applied stack pressure that can prevent both contact loss and SE fracture, which can be extended to other metal-electrode (such as Sodium) SSB systems.
Despite recent significant developments of Si composites, use of silicon with significance in the anodes for Li-ion batteries is still limited. In fact, nominal energy density is to be saturated around ~750 Wh/L regardless of cell-types under the current material strategies. Use of Si-rich anode can push the limit; however, the prolonged irreversible Li consumption becomes more prominent. We previously showed that repeating c-Li3.75(+{delta})Si formation/decomposition, typically recognized to degrade the anodes, can improve the irreversibility and accumulatively minimize the gross consumption. Utilizing the insights combined with prelithiation techniques, here we provide prototypic cell designs that can nonlinearly deplete the consumption.
Solid state electrolytes are widely considered as the enabler of lithium metal anodes for safe, durable and high energy density rechargeable lithium ion batteries. Despite the promise, failure mechanisms associated with solid state batteries are not well-established, largely due to limited understanding of the chemomechanical factors governing them. We focus on the recent developments in understanding the solid state aspects including the effects of mechanical stresses, constitutive relations, fracture, void formation and outline the gaps in literature. We also provide an overview of the manufacturing and processing of solid state batteries in relation to chemomechanics. The gaps identified provides concrete directions towards the rational design and development of failure resistant solid state batteries.
Solid polymer electrolytes for lithium batteries promise improvements in safety and energy density if their conductivity can be increased. Nanostructured block copolymer electrolytes specifically have the potential to provide both good ionic conductivity and good mechanical properties. This study shows that the previously neglected nanoscale composition of the polymer electrolyte close to the electrode surface has an important effect on impedance measurements, despite its negligible extent compared to the bulk electrolyte. Using standard stainless steel blocking electrodes, the impedance of lithium salt-doped poly(isoprene-b-styrene-b-ethylene oxide) (ISO) exhibited a marked decrease upon thermal processing of the electrolyte. In contrast, covering the electrode surface with a low molecular weight poly(ethylene oxide) (PEO) brush resulted in higher and more reproducible conductivity values, which were insensitive to the thermal history of the device. A qualitative model of this effect is based on the hypothesis that ISO surface reconstruction at the different electrode surfaces leads to a change in the electrostatic double layer, affecting electrochemical impedance spectroscopy measurements. As a main result, PEO-brush modification of electrode surfaces is beneficial for the robust electrolyte performance of PEO-containing block-copolymers and may be crucial for their accurate characterization and use in Li-ion batteries.
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.