ABSTRACT
Solid-state electrolytes overcome many challenges of present-day lithium ion batteries, such as safety hazards and dendrite formation1,2. However, detailed understanding of the involved lithium dynamics is missing due to a lack of in operando measurements with chemical and interfacial specificity. Here we investigate a prototypical solid-state electrolyte using linear and nonlinear extreme-ultraviolet spectroscopies. Leveraging the surface sensitivity of extreme-ultraviolet-second-harmonic-generation spectroscopy, we obtained a direct spectral signature of surface lithium ions, showing a distinct blueshift relative to bulk absorption spectra. First-principles simulations attributed the shift to transitions from the lithium 1 s state to hybridized Li-s/Ti-d orbitals at the surface. Our calculations further suggest a reduction in lithium interfacial mobility due to suppressed low-frequency rattling modes, which is the fundamental origin of the large interfacial resistance in this material. Our findings pave the way for new optimization strategies to develop these electrochemical devices via interfacial engineering of lithium ions.
Subject(s)
Electrolytes , Lithium , Electric Power Supplies , Engineering , SoftwareABSTRACT
An amendment to this paper has been published and can be accessed via a link at the top of the paper.
ABSTRACT
A remaining challenge for the deployment of proton-exchange membrane fuel cells is the limited durability of platinum (Pt) nanoscale materials that operate at high voltages during the cathodic oxygen reduction reaction. In this work, atomic-scale insight into well-defined single-crystalline, thin-film and nanoscale surfaces exposed Pt dissolution trends that governed the design and synthesis of durable materials. A newly defined metric, intrinsic dissolution, is essential to understanding the correlation between the measured Pt loss, surface structure, size and ratio of Pt nanoparticles in a carbon (C) support. It was found that the utilization of a gold (Au) underlayer promotes ordering of Pt surface atoms towards a (111) structure, whereas Au on the surface selectively protects low-coordinated Pt sites. This mitigation strategy was applied towards 3 nm Pt3Au/C nanoparticles and resulted in the elimination of Pt dissolution in the liquid electrolyte, which included a 30-fold durability improvement versus 3 nm Pt/C over an extended potential range up to 1.2 V.
ABSTRACT
Understanding ionic transport across interfaces between dissimilar materials and the intrinsic chemical stability of such interfaces is a fundamental challenge spanning many disciplines and is of particular importance for designing conductive and stable solid electrolytes for solid-state Li-ion batteries. In this work, we establish a surface science-based approach for assessing the intrinsic stability of oxide materials in contact with Li metal. Through a combination of experimental and computational insights, using Nb-doped SrTiO3 (Nb/STO) single crystals as a model system, we were able to understand the impact of crystallographic orientation and surface morphology on the extent of the chemical reactions that take place between surface Nb, Ti, and Sr upon reaction with Li. By expanding our approach to investigate the intrinsic stability of the technologically relevant, polycrystalline Nb-doped lithium lanthanum zirconium oxide (Li6.5La3Zr1.5Nb0.5O12) system, we found that this material reacts with Li metal through the reduction of Nb, similar to that observed for Nb/STO. These results clearly demonstrate the feasibility of our approach to assess the intrinsic (in)stability of oxide materials for solid-state batteries and point to new strategies for understanding the performance of such systems.
ABSTRACT
SrTiO3(110) orientated crystals have been heated to temperatures between 1000 °C and 1200 °C in air, alone or in the presence of powder reservoirs of TiO2 or Sr3Ti2O7. In these conditions, the surface is terminated by two types of atomically flat terraces. One has a relatively higher surface potential and promotes the photochemical reduction of silver (it is photocathodic) and the other has a relatively lower surface potential and promotes the photochemical oxidation of lead (it is photoanodic). Measurements of the step heights between the terraces indicate that the surfaces with different properties have different terminations. By adjusting the time and temperature of the anneal, and in some cases including reservoirs of TiO2 or Sr3Ti2O7, it is possible to change the surface area fraction from 98% photocathodic to 100% photoanodic. The surface is more photocathodic when the annealing temperature is lower, the duration shorter, and if Sr3Ti2O7 is present. The surface is more photoanodic if the temperature is higher, the annealing duration longer, and if TiO2 is present. The results make it possible to control the surface potential and the ratio of photocathodic to photoanodic area on the SrTiO3(110) surface.
ABSTRACT
High-temperature annealing in air is used to produce SrTiO3 (111) surfaces with two types of atomically flat terraces: those that promote photoanodic reactions and those that promote photocathodic reactions. Surface potential measurements show that the photocathodic terraces have a relatively more positive surface potential than the photoanodic terraces. After depositing thin TiO2 films on the surface, from 1 to 13 nm thick, the surface of the film above the photocathodic terraces also has photocathodic properties, similar to those of the bare surface. While a more positive surface potential can be detected on the surface of the thinnest TiO2 films (1 nm thick), it is undetectable for thicker films. The persistence of the localized photocathodic properties on the film surface, even in the absence of a measurable difference in local potential, indicates that the charge associated with specific terraces on the bare SrTiO3 (111) surface remains localized at the TiO2/SrTiO3 interface and that the buried charge influences the motion of photogenerated carriers.
ABSTRACT
In this work, we report a flexible field-effect-transistor (FET) biosensor design based on two-dimensional (2-D) polyaniline (PANI) nanostructure. The flexible biosensor devices were fabricated through a facile and inexpensive method that combines top-down and bottom-up processes. The chemically synthesized PANI nanostructure showed excellent p-type semiconductor properties as well as good compatibility with flexible design. With the 2-D PANI nanostructure being as thin as 80 nm and its extremely large surface-area-to-volume (SA/V) ratio due to the intrinsic properties of PANI chemical synthesis, the developed flexible biosensor exhibited outstanding sensing performance in detecting B-type natriuretic peptide (BNP) biomarkers, and was able to achieve high specificity (averagely 112 folds) with the limit of detection as low as 100 pg/mL. PANI nanostructure under bending condition was also investigated and showed controllable conductance changes being less than 20% with good restorability which may open up the possibility for wearable applications.
