12 research outputs found
An infrared, Raman, and X-ray database of battery interphase components
Further technological advancement of both lithium-ion and emerging battery
technologies can be catalyzed by an improved understanding of the chemistry and
working mechanisms of the solid electrolyte interphases (SEIs) that form at
electrochemically active battery interfaces. However, collecting and
interpreting spectroscopy results of SEIs is difficult for several reasons,
including the chemically diverse composition of SEIs. To address this
challenge, we herein present a vibrational spectroscopy and X-ray diffraction
data library of ten suggested SEI chemical constituents relevant to both
lithium-ion and emerging battery chemistries. The data library includes
attenuated total reflectance Fourier transform infrared spectroscopy, Raman
spectroscopy, and X-ray diffraction data, collected in inert atmospheres
afforded by custom designed sample holders. The data library presented in this
work (and online repository) alleviates challenges with locating related work
that is either diffusely spread throughout the literature, or is non-existent,
and provides energy storage researchers streamlined access to vital
SEI-relevant data that can catalyse future battery research efforts.Comment: JML and RK jointly supervised this work. 26 pages, 8 figures, 8
table
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Synchrotron Near-Field Infrared Nanospectroscopy and Nanoimaging of Lithium Fluoride in Solid Electrolyte Interphases in Li-Ion Battery Anodes
Lithium fluoride (LiF) is a ubiquitous component in the solid electrolyte interphase (SEI) layer in Li-ion batteries. However, its nanoscale structure, morphology, and topology, important factors for understanding LiF and SEI film functionality, including electrode passivity, are often unknown due to limitations in spatial resolution of common characterization techniques. Ultrabroadband near-field synchrotron infrared nanospectroscopy (SINS) enables such detection and mapping of LiF in SEI layers in the far-infrared region down to ca. 322 cm-1 with a nanoscale spatial resolution of ca. 20 nm. The surface sensitivity of SINS and the large infrared absorption cross section of LiF, which can support local surface phonons under certain circumstances, enabled characterization of model LiF samples of varying structure, thickness, surface roughness, and degree of crystallinity, as confirmed by atomic force microscopy, attenuated total reflectance FTIR, SINS, X-ray photoelectron spectroscopy, high-angle annular dark-field, and scanning transmission electron microscopy. Enabled by this approach, LiF within SEI films formed on Cu, Si, and metallic glass Si40Al50Fe10 electrodes was detected and characterized. The nanoscale morphologies and topologies of LiF in these SEI layers were evaluated to gain insights into LiF nucleation, growth, and the resulting nuances in the electrode surface passivity
Understanding the Amorphous Lithiation Pathway of the Type I BaGe Clathrate with Synchrotron X-ray Characterization
Tetrel (Tt = Si, Ge, and Sn) clathrates have highly tunable host–guest structures and have been investigated as novel electrode materials for Li-ion batteries. However, there is little understanding of how the clathrate structure affects the lithiation processes and phase evolution. Herein, the electrochemical lithiation pathway of type I clathrate BaGe is investigated with synchrotron X-ray diffraction (XRD) and pair distribution function (PDF) analyses and compared to the lithiation of germanium with a diamond cubic structure (α-Ge). The results confirm previous laboratory XRD studies showing that BaGe goes through a solely amorphous phase transformation, which contrasts with the crystalline phase transformations that take place during lithiation of micrometer-sized α-Ge particles. The local structure of framework-substituted clathrate BaAlGe after lithiation is found to proceed through an amorphous phase transformation similar to that in BaGe. In situ PDF and XRD during heating show that the amorphous phases derived from lithiation of BaGe are structurally related to various Li–Ge phases and crystallize at low temperatures (350–420 K). We conclude that the Ba atoms inside the clathrate structure act to break up the long-range ordering of Li–Ge clusters and kinetically prevent the nucleation and growth of bulk crystalline phases. The amorphous phase evolution of the clathrate structure during lithiation results in electrochemical properties distinct from those in α-Ge, such as a single-phase reaction mechanism and lower voltage, suggesting possible advantages of clathrates over elemental phases for use as anodes in Li-ion batteries
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Nano-FTIR Spectroscopy of the Solid Electrolyte Interphase Layer on a Thin-Film Silicon Li-Ion Anode.
Si anodes for Li-ion batteries are notorious for their large volume expansion during lithiation and the corresponding detrimental effects on cycle life. However, calendar life is the primary roadblock for widespread adoption. During calendar life aging, the main origin of impedance increase and capacity fade is attributed to the instability of the solid electrolyte interphase (SEI). In this work, we use ex situ nano-Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy to characterize the structure and composition of the SEI layer on amorphous Si thin films after an accelerated calendar aging protocol. The characterization of the SEI on non-washed and washed electrodes shows that brief washing in dimethyl carbonate results in large changes to the film chemistry and topography. Detailed examination of the non-washed electrodes during the first lithiation and after an accelerated calendar aging protocol reveals that PF6- and its decomposition products tend to accumulate in the SEI due to the preferential transport of PF6- ions through polyethylene oxide-like species in the organic part of the SEI layer. This work demonstrates the importance of evaluating the SEI layer in its intrinsic, undisturbed form and new strategies to improve the passivation of the SEI layer are proposed
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Oxygen Transport through Amorphous Cathode Coatings in Solid-State Batteries.
All solid-state batteries (SSBs) are considered the most promising path to enabling higher energy-density portable energy, while concurrently improving safety as compared to current liquid electrolyte solutions. However, the desire for high energy necessitates the choice of high-voltage cathodes, such as nickel-rich layered oxides, where degradation phenomena related to oxygen loss and structural densification at the cathode surface are known to significantly compromise the cycle and thermal stability. In this work, we show, for the first time, that even in an SSB, and when protected by an intact amorphous coating, the LiNi0.5Mn0.3Co0.2O2 (NMC532) surface transforms from a layered structure into a rocksalt-like structure after electrochemical cycling. The transformation of the surface structure of the Li3B11O18 (LBO)-coated NMC532 cathode in a thiophosphate-based solid-state cell is characterized by high-resolution complementary electron microscopy techniques and electron energy loss spectroscopy. Ab initio molecular dynamics corroborate facile transport of O2- in the LBO coating and in other typical coating materials. This work identifies that oxygen loss remains a formidable challenge and barrier to long-cycle life high-energy storage, even in SSBs with durable, amorphous cathode coatings, and directs attention to considering oxygen permeability as an important new design criteria for coating materials
Structural Origin of Reversible Li Insertion in Guest‐Free, Type‐II Silicon Clathrates
The guest-free, type-II Si clathrate (Si) is an open cage polymorph of Si with structural features amenable to electrochemical Li storage. However, the detailed mechanism for reversible Li insertion and migration within the vacant cages of Si is not established. Herein, X-ray characterization and density functional theory (DFT) calculations are used to understand the structural origin of electrochemical Li insertion into the type-II clathrate structure. At low Li content, instead of alloying with Si, topotactic Li insertion into the empty cages occurs at ≈0.3 V versus Li/Li with a capacity of ≈231 mAh g (corresponding to composition LiSi). A synchrotron powder X-ray diffraction analysis of electrodes after lithiation shows evidence of Li occupation within the Si and Si cages and a volume expansion of 0.22%, which is corroborated by DFT calculations. Nudged elastic band calculations suggest a low barrier (0.2 eV) for Li migration through interconnected Si cages, whereas there is a higher barrier for Li migration into Si cages (2.0 eV). However, if Li is present in a neighboring cage, a cooperative migration pathway with a barrier of 0.65 eV is possible. The results show that the type-II Si clathrate displays unique electrochemical properties for potential applications as Li-ion battery anodes
Layered Double Hydroxide/Chitosan Nanocomposite Beads as Sorbents for Selenium Oxoanions
Layered
double hydroxide (LDH) nanoparticles are effective sorbents
for selenium oxoanions but must be fabricated in a suitable fashion
for implementation in water treatment applications using packed columns.
In this work, we demonstrate the preparation of nanocomposite beads
prepared from Mg–Al–CO<sub>3</sub> LDH nanoparticles
and chitosan, a sustainable and biodegradable biopolymer. The synthesis
of the nanocomposite beads is achieved by direct mixing or in situ
synthesis of the LDH nanoparticles into the chitosan matrix. The effect
of the preparation route on the nanocomposite structure, maximum loading
of LDH in the composite, removal kinetics, and the maximum sorption
capabilities for selenate and selenite oxoanions are studied and compared
to LDH nanopowders and granular media. The results indicate that the
in situ synthesis of LDH inside the beads leads to several favorable
characteristics such as a higher mass loading of LDH and better dispersion
of the nanoparticles while displaying good selenium removal over a
wide pH range, superior sorption capacities to the nanopowder, and
sorption kinetics similar to those of the granulated media. The maximum
adsorption capacities for the nanocomposite beads from Langmuir isotherms
were 17 mg/g for Se(IV) and ∼12 mg/g for Se(VI) with respect
to the mass of LDH, which is higher than reported capacities obtained
in chitosan beads embedded with other nanocrystalline metal oxide
fillers. These results show that the LDH/chitosan nanocomposite beads
are promising alternatives to granulated media for selenium removal
and sheds light on how best to design and fabricate high performance
and sustainable nanoenabled sorbents for water treatment applications
Layered Double Hydroxide Sorbents for Removal of Selenium from Power Plant Wastewaters
Selenium is an essential trace element but is increasingly becoming a contaminant of concern in the electric power industry due to the challenges of removing solubilized selenate anions, particularly in the presence of sulfate. In this work, we evaluate granulated layered double hydroxide (LDH) materials as sorbents for selenium removal from wastewaters obtained from a natural gas power plant with the aim to elucidate the effect of competing ions on the sorption capacities for selenium removal. We first present jar test data, followed by small-scale column testing in 0.43 inch (1.1 cm) and 2 inch (5.08 cm) diameter testbed columns for the treatment of as-obtained cooling tower blowdown waters and plant wastewaters. Finally, we present field results from a pilot-scale study evaluating the LDH media for treatment of cooling tower blowdown water. We find that despite the high levels of total dissolved solids and competing sulfate ions, the selenium oxoanions and other regulated metals such as chromium and arsenic are successfully removed using LDH media without needing any pre-treatment or pH adjustment of the wastewater