اشترك بالحزمة الذهبية واحصل على وصول غير محدود شمرا أكاديميا
تسجيل مستخدم جديدFavorable Interfacial Chemomechanics Enables Stable Cycling of High Li-Content Li-In/Sn Anodes in Sulfide Electrolyte Based Solid-State Batteries
172
0
0.0
(
0
)
اسأل ChatGPT حول البحث
ﻻ يوجد ملخص باللغة العربية
Solid-state batteries (SSBs) can offer a paradigm shift in battery safety and energy density. Yet, the promise hinges on the ability to integrate high-performance electrodes with state-of-the-art solid electrolytes. For example, lithium (Li) metal, the most energy-dense anode candidate, suffers from severe interfacial chemomechanical issues that lead to cell failure. Li alloys of In/Sn are attractive alternatives, but their exploration has mostly been limited to the low capacity(low Li content)and In rich Li$_x$In (x$leq$0.5). Here, the fundamental electro-chemo-mechanical behavior of Li-In and Li-Sn alloys of varied Li stoichiometries is unravelled in sulfide electrolyte based SSBs. The intermetallic electrodes developed through a controlled synthesis and fabrication technique display impressive (electro)chemical stability with Li$_6$PS$_5$Cl as the solid electrolyte and maintain nearly perfect interfacial contact during the electrochemical Li insertion/deinsertion under an optimal stack pressure. Their intriguing variation in the Li migration barrier with composition and its influence on the observed Li cycling overpotential is revealed through combined computational and electrochemical studies. Stable interfacial chemomechanics of the alloys allow long-term dendrite free Li cycling (>1000 h) at relatively high current densities (1 mA cm$^{-2}$) and capacities (1 mAh cm$^{-2}$), as demonstrated for Li$_{13}$In$_3$ and Li$_{17}$Sn$_4$, which are more desirable from a capacity and cost consideration compared to the low Li content analogues. The presented understanding can guide the development of high-capacity Li-In/Sn alloy anodes for SSBs.
قيم البحث
اقرأ أيضاً
The development of silicon anodes to replace conventional graphite in efforts to increase energy densities of lithium-ion batteries has been largely impeded by poor interfacial stability against liquid electrolytes. Here, stable operation of 99.9 wei
ght% micro-Si (uSi) anode is enabled by utilizing the interface passivating properties of sulfide based solid-electrolytes. Bulk to surface characterization, as well as quantification of interfacial components showed that such an approach eliminates continuous interfacial growth and irreversible lithium losses. In uSi || layered-oxide full cells, high current densities at room temperature (5 mA cm 2), wide operating temperature (-20{deg}C to 80{deg}C) and high loadings (>11 mAh cm-2) were demonstrated for both charge and discharge operations. The promising battery performance can be attributed to both the desirable interfacial property between uSi and sulfide electrolytes, as well as the unique chemo-mechanical behavior of the Li-Si alloys.
For a successful integration of silicon in high-capacity anodes of Li-ion batteries, its intrinsic capacity decay on cycling due to severe volume swelling should be minimized. In this work, Ni-Sn intermetallics are studied as buffering matrix during
reversible lithiation of Si-based anodes. Si/Ni-Sn composites have been synthetized by mechanical milling using C and Al as process control agents. Ni3Sn4, Ni3Sn2 intermetallics and their bi-phasic mixture were used as constituents of the buffering matrix. The structure, composition and morphology of the composites have been analyzed by X-ray diffraction (XRD), 119Sn Transmission Mossbauer Spectroscopy (TMS) and scanning electron microscopy (SEM). They consist of ~ 150 nm Si nanoparticles embedded in a multi-phase matrix, the nanostructuration of which improves on increasing the Ni3Sn4 amount. The electrochemical properties of the composites were analyzed by galvanostatic cycling in half-cells. Best results for practical applications are found for the bi-phasic matrix Ni3Sn4-Ni3Sn2 in which Ni3Sn4 is electrochemically active while Ni3Sn2 is inactive. Low capacity loss, 0.04 %/cycle, and high coulombic efficiency, 99.6%, were obtained over 200 cycles while maintaining a high reversible capacity above 500 mAh/g at moderate regime C/5
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 dep
osition 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.
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 interphas
e (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.
We study the oxo-hexametallate Li$_7$TaO$_6$ with first-principles and classical molecular dynamics simulations, obtaining a low activation barrier for diffusion of $sim$0.29 eV and a high ionic conductivity of $5.7 times 10^{-4}$ S cm$^{-1}$ at room
temperature (300 K). We find evidence for a wide electrochemical stability window from both calculations and experiments, suggesting its viable use as a solid-state electrolyte in next-generation solid-state Li-ion batteries. To assess its applicability in an electrochemical energy storage system, we performed electrochemical impedance spectroscopy measurements on multicrystalline pellets, finding substantial ionic conductivity, if below the values predicted from simulation. We further elucidate the relationship between synthesis conditions and the observed ionic conductivity using X-ray diffraction, inductively coupled plasma optical emission spectrometry, and X-ray photoelectron spectroscopy, and study the effects of Zr and Mo doping.
سجل دخول لتتمكن من نشر تعليقات
التعليقات
جاري جلب التعليقات
سجل دخول لتتمكن من متابعة معايير البحث التي قمت باختيارها
