اشترك بالحزمة الذهبية واحصل على وصول غير محدود شمرا أكاديميا
تسجيل مستخدم جديدModulating nano-inhomogeneity at electrode-solid electrolyte interfaces for dendrite-proof solid-state batteries and long-life memristors
60
0
0.0
(
0
)
اسأل ChatGPT حول البحث
ﻻ يوجد ملخص باللغة العربية
The penetration of dendrites in ceramic lithium conductors severely constrains the development of solid-state batteries (SSBs) while its nanoscopic origin remain unelucidated. We develop an in-situ nanoscale electrochemical characterization technique to reveal the nanoscopic lithium dendrite growth kinetics and use it as a guiding tool to unlock the design of interfaces for dendrite-proof SSBs. Using Li7La3Zr2O12 (LLZO) as a model system, in-situ nanoscopic dendrite triggering measurements, ex-situ electro-mechanical characterizations, and finite element simulations are carried out which reveal the dominating role of Li+ flux detouring and nano-mechanical inhomogeneity on dendrite penetration. To mitigate such nano-inhomogeneity, an ionic-conductive homogenizing layer based on poly(propylene carbonate) is designed which in-situ reacts with lithium to form a highly conformal interphase at mild conditions. A high critical current density of 1.8mA cm-2 and a low interfacial resistance of 14{Omega} cm2 is achieved. Practical SSBs based on LiFePO4 cathodes show great cyclic stability without capacity decay over 300 cycles. Beyond this, highly reversible electrochemical dendrite healing behavior in LLZO is discovered using the nano-electrode, based on which a model memristor with a high on/off ratio of ~10^5 is demonstrated for >200 cycles. This work not only provides a novel tool to investigate and design interfaces in SSBs but offers also new opportunities for solid electrolytes beyond energy applications.
قيم البحث
اقرأ أيضاً
Near total reflection regime has been widely used in X-ray science, specifically in grazing incidence small angle X-ray scattering and in hard X-ray photoelectron spectroscopy. In this work, we introduce some practical aspects of using near total ref
lection in ambient pressure X-ray photoelectron spectroscopy and apply this technique to study chemical concentration gradients in a substrate/photoresist system. Experimental data are accompanied by X-ray optical and photoemission simulations to quantitatively probe the photoresist and the interface with the depth accuracy of ~1 nm. Together, our calculations and experiments confirm that near total reflection X-ray photoelectron spectroscopy is a suitable method to extract information from buried interfaces with highest depth-resolution, which can help address open research questions regarding our understanding of concentration profiles, electrical gradients, and charge transfer phenomena at such interfaces. The presented methodology is especially attractive for solid/liquid interface studies, since it provides all the strengths of a Bragg-reflection standing-wave spectroscopy without the need of an artificial multilayer mirror serving as a standing wave generator, thus dramatically simplifying the sample synthesis.
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.
Several active areas of research in novel energy storage technologies, including three-dimensional solid state batteries and passivation coatings for reactive battery electrode components, require conformal solid state electrolytes. We describe an at
omic layer deposition (ALD) process for a member of the lithium phosphorus oxynitride (LiPON) family, which is employed as a thin film lithium-conducting solid electrolyte. The reaction between lithium tert-butoxide (LiO$^t$Bu) and diethyl phosphoramidate (DEPA) produces conformal, ionically conductive thin films with a stoichiometry close to Li$_2$PO$_2$N between 250 and 300$^circ$C. The P/N ratio of the films is always 1, indicative of a particular polymorph of LiPON which closely resembles a polyphosphazene. Films grown at 300$^circ$C have an ionic conductivity of $6.51:(pm0.36)times10^{-7}$ S/cm at 35$^circ$C, and are functionally electrochemically stable in the window from 0 to 5.3V vs. Li/Li$^+$. We demonstrate the viability of the ALD-grown electrolyte by integrating it into full solid state batteries, including thin film devices using LiCoO$_2$ as the cathode and Si as the anode operating at up to 1 mA/cm$^2$. The high quality of the ALD growth process allows pinhole-free deposition even on rough crystalline surfaces, and we demonstrate the fabrication and operation of thin film batteries with the thinnest (<100nm) solid state electrolytes yet reported. Finally, we show an additional application of the moderate-temperature ALD process by demonstrating a flexible solid state battery fabricated on a polymer substrate.
Lithium metal penetrations through the liquid-electrolyte-wetted porous separator and solid electrolytes are a major safety concern of next-generation rechargeable metal batteries. The penetrations were frequently discovered to occur through only a f
ew isolated channels, as revealed by black spots on both sides of the separator or electrolyte, which manifest a highly localized ionic flux or current density. Predictions of the penetration time have been infeasible due to the hidden and unclear dynamics in these penetration channels. Here, using the glass capillary cells, we investigate for the first time the unexpectedly sensitive influence of channel geometry on the concentration polarization and dendrite initiation processes. The characteristic time for the complete depletion of salt concentration on the surface of the advancing electrode, i.e. Sands time, exhibits a nonlinear dependence on the curvature of the channel walls along the axial direction. While a positively deviated Sands time scaling exponent can be used to infer a converging penetration area through the electrolyte, a negatively deviated scaling exponent suggests that diffusion limitation can be avoided in expanding channels, such that the fast-advancing tip-growing dendrites will not be initiated. The safety design of rechargeable metal batteries will benefit from considering the true local current densities and the conduction structures.
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.
سجل دخول لتتمكن من نشر تعليقات
التعليقات
جاري جلب التعليقات
سجل دخول لتتمكن من متابعة معايير البحث التي قمت باختيارها
