The effect of the electrolyte additive fluoroethylene carbonate (FEC) for Li-ion batteries has been widely discussed in literature in recent years. Here, the additive is studied for the high-voltage cathode LiNi0.5Mn1.5O4 (LNMO) coupled to Li4Ti5O12 (LTO) to specifically study its effect on the cathode side. Electrochemical performance of full cells prepared by using a standard electrolyte (LP40) with different concentrations of FEC (0, 1 and 5 wt%) were compared and the surface of cycled positive electrodes were analyzed by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The results show that addition of FEC is generally of limited use for this battery system. Addition of 5 wt% FEC results in relatively poor cycling performance, while the cells with 1 wt% FEC showed similar behavior compared to reference cells prepared without FEC. SEM and XPS analysis did not indicate the formation of thick surface layers on the LNMO cathode, however, an increase in layer thickness with increased FEC content in the electrolyte could be observed. XPS analysis on LTO electrodes showed that the electrode interactions between positive and negative electrodes occurred as Mn and Ni were detected on the surface of LTO already after 1 cycle. (C) The Author(s) 2017. Published by ECS. All rights reserved.
Electrochromic (EC) films of nickel oxide, with and without vanadium, were prepared by reactive dc magnetron sputtering. They were characterized by electrochemical and optical measurements and studied by X-ray photoelectron spectroscopy (PES) using synchrotron radiation. The films were analyzed under as-deposited conditions and after bleaching/coloration by insertion/extraction of protons from a basic solution and ensuing charge stabilization. Optical measurements were consistent with a coloration process due to charge-transfer transitions from Ni2+ to Ni3+ states. The PES measurements showed a higher concentration of Ni3+ in the colored films. Moreover, two peaks were present in the O 1s spectra of the bleached film and pointed to contributions of Ni(OH)(2) and NiO. The changes in the O 1s spectra upon coloration treatment indicate the presence of Ni2O3 in the colored film and necessitated an extension of the conventional model for the mechanism of EC coloration. The model involves not only proton extraction from nickel hydroxide to form nickel oxyhydroxide but also participation of NiO in the coloration process to form Ni2O3.
The cycle life of LiNi1/3Co1/3Mn1/3O2 (NMC) based cells are significantly influenced by the choice of the negative electrode. Electrochemical testing and post mortem surface analysis are here used to investigate NMC electrodes cycled vs. either Li-metal, graphite or Li4Ti5O12 (LTO) as negative electrodes. While NMC-LTO and NMC-graphite cells show small capacity fading over 200 cycles, NMC-Li-metal cell suffers from rapid capacity fading accompanied with an increased voltage hysteresis despite the almost unlimited access of lithium. X-ray absorption near edge structure (XANES) results show that no structural degradation occurs on the positive electrode even after >200 cycles, however, X-ray photoelectron spectroscopy (XPS) results shows that the composition of the surface layer formed on the NMC cathode in the NMC-Li-metal cell is largely different from that of the other NMC cathodes (cycled in the NMC-graphite or NMC-LTO cells). Furthermore, it is shown that the surface layer thickness on NMC increases with the number of cycles, caused by continuous electrolyte degradation products formed at the Li-metal negative electrode and then transferred to NMC positive electrode.
The performance of lithium-ion batteries (LIBs) comprising SnO2 electrodes and an ionic liquid (IL) based electrolyte, i.e., 0.5 MLiTFSI in Pip14TFSI, has been studied at room temperature (i.e., 22◦C) and 80◦C. While the high viscosity and low conductivity ofthe electrolyte resulted in high overpotentials and low capacities at room temperature, the SnO2 performance at 80◦C was found to beanalogous to that seen at room temperature using a standard LP40 electrolyte (i.e., 1MLiPF6 dissolved in 1:1 ethylene carbonate anddiethyl carbonate). Significant reduction of the IL was, however, found at 80◦C, which resulted in low coulombic efficiencies duringthe first 20 cycles, most likely due to a growing SEI layer and the formation of soluble IL reduction products. X-ray photoelectronspectroscopy studies of the cycled SnO2 electrodes indicated the presence of an at least 10 nm thick solid electrolyte interphase (SEI)layer composed of inorganic components such as lithium fluoride, sulfates, and nitrides as well as organic species containing C-H,C-F and C-N bonds.
Materials that undergo ion-insertion coupled electron transfer are important for energy storage, energy conversion, and optoelectronics applications. Cyclic voltammetry is a powerful technique to understand electrochemical kinetics. However, the interpretation of the kinetic behavior of ion insertion electrodes with analytical solutions developed for ion blocking electrodes has led to confusion about their rate-limiting behavior. The purpose of this manuscript is to demonstrate that the cyclic voltammetry response of thin film electrode materials undergoing solid-solution ion insertion without significant Ohmic polarization can be explained by well-established models for finite diffusion. To do this, we utilize an experimental and simulation approach to understand the kinetics of Li+ insertion-coupled electron transfer into a thin film material (Nb2O5). We demonstrate general trends for the peak current vs scan rate behavior, with the latter parameter elevated to an exponent between limiting values of 1 and 0.5, depending on the solid-state diffusion characteristics of the film (diffusion coefficient, film thickness) and the experiment timescale (scan rate). We also show that values < 0.5 are possible depending on the cathodic potential limit. Our results will be useful to fundamentally understand and guide the selection and design of intercalation materials for multiple applications.
This work aims to address two major roadblocks in the development of lithium-sulfur (Li-S) batteries: the inefficient deposition of Li on the metallic Li electrode and the parasitic "polysulfide redox shuttle". These roadblocks are here approached, respectively, by the combination of a cellulose separator with a cathode-facing conductive porous carbon interlayer, based on their previously reported individual benefits. Both approaches result in significant improvements in cycle life in test cells with positive electrodes with practically relevant specifications. Despite the substantially prolonged cycle life, the combination of the interlayer and cellulose separator generates an increase in polysulfide shuttle current, leading to greatly reduced Coulombic efficiency. Based on XPS analyses, the latter is ascribed to a change in the composition of the solid electrolyte interphase (SEI) on the Li electrode. At the same time, the rate of electrolyte decomposition is found to be lower in cells with cellulose-based separators, which corroborates the observation of longer cycle life. These seemingly contradictory and counterintuitive observations demonstrate the complicated interactions between the cell components in the Li-S system and how strategies aiming to mitigate one unwanted process may exacerbate another. This study demonstrates the value of a holistic approach to the development of Li-S chemistry.
Amorphous or cubic Gd2O3 thin films were grown from tris ( 2,3-dimethyl-2-butoxy)gadolinium( III) , Gd [OC(CH3)(2)CH(CH3)(2))(3)], and H2O precursors at 350 degrees C. As-deposited Gd2O3 films grown on etched (H-terminated) Si(100) exhibited better leakage current-voltage characteristics as well as lower flatband voltage shift than films grown on SiO2/ Si substrates. Interface trap densities were lower in Al/Gd2O3/ hydrofluoric acid (HF)-etched Si samples annealed at rather high temperatures.
In a previous work [El-Tahawy et al., J. Magn. Magn. Mater. 560, 169660 (2022)], we reported that from a sulfate type bath, hcp-Co can be electrodeposited at high pH and low current density and investigated the structure and magnetoresistance (MR) characteristics of such hcp-Co electrodeposits. Based on this earlier work, Co-rich Co-Cu and Co-Ni alloy electrodeposits were prepared under the same conditions by adding varying amounts of CuSO4 and NiSO4, respectively, to the CoSO4 bath. According to the results of detailed structural studies by various X-ray diffraction (XRD) geometries, in both the Co-Cu and Co-Ni systems an hcp phase formed exclusively up to about 2 at% of the alloying element. Above this concentration, a significant fcc phase fraction appeared in Co-Cu and a minor fcc fraction in Co-Ni up to about 8 at%. This means that the destabilization effect of Cu on hcp-Co is higher than that of Ni. Although the reduction of the stability of hcp-Co with increasing Cu and Ni content is a well-known phenomenon, a quantitative comparison of this effect in Co-Cu and Co-Ni alloys is missing from the literature. The measured lattice constants are analyzed in comparison with Vegard's law for the Co-Cu and Co-Ni element pairs deduced from data previously reported for the hcp and fcc phases of all three pure elements. For Co-rich Co-Ni alloys, the concentration dependence of the lattice parameters was found to follow Vegard's law for both the hcp and fcc phases due to the miscibility of the two components. For the Co-rich Co-Cu alloys, the data indicate a positive deviation from Vegard's law for both the hcp and fcc phases in agreement with the known similar behavior of fcc Co-Cu alloys for the whole composition range. The positive deviation from Vegard's law in the Co-Cu system is due to the excess mixing volume required for solid solution alloy formation of these immiscible elements in either phases. The MR data are discussed in the light of the observed phases and of the MR parameters reported in our previous work on the hcp and fcc phases of pure Co.
While solid polymer electrolytes (SPEs) have great potential for use in future lithium-based batteries, they do, however, not display conductivity at a sufficient level as compared to liquid electrolytes. To reach the needed requirements of lithium batteries it is therefore necessary to explore new materials classes to serve as novel polymer hosts. In this work, SPEs based on the polyketone poly(3,3-dimethylpentane-2,4-dione) were investigated. Polyketones are structurally similar to several polycarbonate and polyester SPE hosts investigated before but have, due to the lack of additional oxygen atoms in the coordinating motif, even more electronwithdrawing carbonyl groups and could therefore display better properties for coordination to the salt cation. In electrolyte compositions comprising 25-40 wt% LiTFSI salt, it was observed that this polyketone indeed conducts lithium ions with a high cation transference number, but that the ionic conductivity is limited by the semi-crystallinity of the polymer matrix. The crystallinity decreases with increasing salt content, and a fully amorphous SPE can be produced at 40 wt% salt, accompanied by an ionic conductivity of 3 x 10(-7) S cm(-1) at 32 degrees C. This opens up for further exploration of polyketone systems for SPE-based batteries.
The interface chemistry of LixMn2O4 electrodes in carbonate-based electrolytes has been investigated using X-ray photoelectron spectroscopy, infrared spectroscopy, Raman spectroscopy, and scanning electron microscopy following cycling or storage in ⟨LiMn2O4| ethylene carbonate/dimethyl carbonate LiPF6/LiBF4|Li⟩ cells. No significant changes were found in the elemental composition of surface films formed on cycled and stored samples, suggesting that surface-film formation is not governed by processes associated with cell cycling. The amount of surface species increases with storage time and cycle number at ambient temperature, where LiF, LixPFyOz products and some polyether-type polymeric compound could be identified as reaction products on the cathode surface. A lithium-rich manganese oxide layer develops on the surface of the cathode particles under continued storage and cycling. The thickness of the surface layer decreases rather than increases with storage at a higher state-of-charge. More carbon compounds are preserved on the electrode surface using LiBF4 rather than LiPF6 as electrolyte salt.
Nanolayers of Cu and Cu2O with a wide range of layer thicknesses have been produced using pulsed galvanostatic and potentiostatic electrodeposition from alkaline Cu(II)-citrate solutions. The thicknesses of the individual Cu and Cu2O layers can be independently controlled and the composition of the multilayered materials, which also were studied using electrochemical quartz crystal microbalance, X-ray diffraction, and scanning electron microscopy, can be varied from pure Cu to pure Cu2O by varying the current density or the deposition potential. It is shown that some of the deposited Cu2O is reduced during the subsequent copper deposition step and that the influence of this effect depends on the Cu (II) concentration, the Cu2O microstructure, and the deposition mode. Additional Cu2O deposition is demonstrated to take place after the copper deposition step due to comproportionation and precipitation of Cu2O. This effect facilitates electrodeposition of Cu2O on Cu. Deposition of Cu on the Cu2O layer formed by comproportionation and precipitation was likewise found to be more straightforward than on electrodeposited Cu2O. Well-defined nanolayered Cu/Cu2O materials are generally best manufactured using pulsed galvanostatic techniques because a much larger fraction of the Cu2O was found to be reduced during the subsequent Cu deposition pulse in pulsed potentiostatic depositions.
Hybrid gas sensors were fabricated by means of multiwalled carbon nanotubes (MWCNTs) covered by W O3 deposited by an advanced reactive gas deposition method. In order to increase the dispersion of nanotubes and attach functional groups to their surface so as to enhance their compatibility with other compounds, the MWCNTs were functionalized in two different radio-frequency plasmas (oxygen or hydrogen) under different operating conditions. X-ray photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy were employed to analyze the composition and morphology of the hybrid films. Gas sensors based on such films were found to be very selective to N O2 when operated at room temperature. No cross-sensitivity was found to other hazardous gases such as N H3 or CO.
We have investigated atmospheric corrosion of a 50 nm layer of iron covered with a thin layer of NaCl by in situ X-ray transmission spectromicroscopy. We find that upon its deliquescence, a small part of the NaCl layer is rapidly transformed into a sodium oxide (NaOH) species. A large part of the sodium and chlorine ions forms a concentrated solution on the iron surface and becomes segregated, whereby the sodium ions appear stationary and passive during further corrosion progression. In contrast, the chlorine ions appear highly mobile and become concentrated at and travel with the corrosion front, apparently acting as a corrosion catalyst. The corrosion front progression is partly of filiform and partly of radial type. The early iron corrosion products (chloride-containing oxyhydroxides) are short-lived (for some hours) and undergo a transformation as the corrosion front sweeps by from a chlorinated species to a less chlorinated species.
This study describes deposition of HfO2 thin films by chemical vapor deposition (CVD) and atomic layer deposition (ALD) using HfI4 as the metal precursor. The layer-by-layer growth was also studied in real time with a quartz crystal microbalance. In ALD, the deposition rate was independent of the growth temperature, whereas in CVD, an exponential rate increase was observed. Monoclinic HfO2 was deposited on MgO and poly-Si substrates in a wide temperature range, and the choice of substrate had a strong influence on the orientation of the films. Epitaxial growth of HfO2 was observed on MgO(001) substrates at 400-500°C in the ALD process and at 500-600°C in the CVD process. The electrical characterization showed that the crystallinity of the films had a stronger influence on the dielectric constant than did the film thickness.
Electron and Li ion conducting properties of room temperature sputtered amorphous tantalum oxide (a-Ta2O5) films were studied in order to evaluate the feasibility of using a-Ta2O5 in electrochromic device applications. The films were investigated using the galvanostatic intermittent titration technique, impedance spectroscopy, and isothermal transient ionic current measurements. It was found that the a-Ta2O5 met two out of three requirements posed on a Li ion conductor in a WO3 based electrochromic device. There was a negligible intercalation in the potential window used in WO3-based electrochromic devices (above 2.4-2.5 V vs. Li/Li+). Furthermore, in this potential region, the chemical diffusion coefficient for Li was larger than the corresponding quantity in WO3. However, there was a nonzero electron conductivity in the a-Ta2O5 films, not observed in the chemical vapor deposition-made β-Ta2O5 investigated earlier. Still, the ionic conductivity was approximately one order of magnitude larger than the electronic one.
Solid polymer electrolytes (SPEs) are promising candidates for solid-state lithium-ion batteries. Potentially, they can be used with lithium metal anodes and high-voltage cathodes, provided that their electrochemical stability is sufficient. Thus far, the oxidative stability has largely been asserted based on results obtained with sweep voltammetry, which are often determined and reliant on arbitrary assessments that are highly dependent on the experimental conditions and do not take the interaction between the electrolyte and the electrode material into account. In this study, alternative techniques are introduced to address the pitfalls of sweep voltammetry for determining the oxidative stability of SPEs. Staircase voltammetry involves static conditions and eliminates the kinetic aspects of sweep voltammetry, and coupled with impedance spectroscopy provides information of changes in resistance and interphase layer formation. Synthetic charge–discharge profile voltammetry applies the real voltage profile of the active material of interest. The added effect of the electrode active material is investigated with a cut-off increase cell cycling method where the upper cut-off voltage during galvanostatic cycling is gradually increased. The feasibility of these techniques has been tested with both poly(ethylene oxide) and poly(trimethylene carbonate) combined with LiTFSI, thereby showing the applicability for several categories of SPEs.
We present a study of the charge-state behavior of the Li-ion battery cathode material LixNi(0.65)Co(0.25)Mn(0.1)O(2) as observed by X-ray absorption spectroscopy (XAS) and resonant soft X-ray emission (RSXE). A set of six identical Li//LixNi0.65Co0.25Mn0.1O2 batteries has been cycled and is studied in different states of charge in the range of x = 1.0, ... ,0.2 before disassembly in an Ar glove box. Site and symmetry selective information about the electronic structure of the conduction and valence bands reveals that Ni as well as Co ions participate in the uptake and release of the extra electron charge that the inserted Li ions provide, but the Ni ion is much less than expected. The net amount of charge on the oxygen varies approximately 0.24 charge units in the range of x, and dramatic changes in the hybridization are evident in XAS and in particular in RSXE at the O K edge. We attribute this to a strong screening behavior of the Li ions between the oxide layers. Structural integrity effects limit the extraction of Li ions to a value of about x = 0.2-0.4. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3454739] All rights reserved.
We present results from X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) of oxidized polycrystalline copper surfaces [Cu(I) and Cu(II), respectively] exposed to a 1.0 mM aqueous solution of Na2S (sodium sulfide) for several hours. Scanning electron microscopy reveals that the Cu oxide surfaces attain a much rougher texture upon sodium sulfide exposure, and that the exposed Cu(II) oxide sample exhibits areas with crystallites. The XAS spectra show that sodium sulfide effectively reduces Cu(II) oxide to Cu(I) compounds. The RIXS spectra of the exposed surfaces closely resemble those of the Cu2O reference sample with the notable exception of their Cu LIII,II-RIXS spectra. We conclude that copper evidently forms a Cu(I) compound with oxygen but with a Cu 3d-band of much reduced width, pointing to the possibility of a more complex compound containing both oxygen and sulfur.
Poly(vinylidene-difluoride) (PVdF) based polymers constitute the most commonly used binders for lithium-ion battery electrodes. In scientific studies, the binder content often exceeds commercially meaningful amounts. At the same time, the battery electrode performance can in various ways be coupled to its binder content, partly due to its influence on the surface properties. For example, an optimum binder content of around 5 wt% has been reported. In this study, graphite: PVdF-HFP electrodes containing 2.5, 5 and 10 wt% of PVdF-HFP are investigated, and their electrochemical behavior are put into context of the electrode-electrolyte interphase of the different formulations. Although the electrodes display similar electrochemical behavior, the SEI layer composition and thickness, analyzed by photoelectron spectroscopy, vary notably depending on binder content. It was found that a binder content of 5 wt% maintained the best cycling stability and also exhibited a thinner SEI layer with a larger fraction of inorganic components. In contrast to higher binder contents, where the binder covers most of the surface, larger parts of the active material are exposed directly to the electrolyte with binder contents of 2.5-5 wt%. The formation of a thinner, yet protective, SEI layer is beneficial for cycling performance of the graphite electrode. (C) 2017 The Electrochemical Society. All rights reserved.
Atomic layer deposition (ALD) of ZrO2-Gd2O3 nanolaminates and mixtures was investigated for the preparation of a high permittivity dielectric material. Variation in the relative number of ALD cycles for constituent oxides allowed one to obtain films with controlled composition. Pure ZrO2 films possessed monoclinic and higher permittivity cubic or tetragonal phases, whereas the inclusion of Gd2O3 resulted in the disappearance of the monoclinic phase. Changes in phase composition were accompanied with increased permittivity of mixtures and laminates with low Gd content. Further increase in the lower permittivity Gd2O3 content above 3.4 cat. % resulted in the decreased permittivity of the mixtures. Leakage currents generally decreased with increasing Gd content, whereby laminated structures demonstrated smaller leakage currents than mixed films at a comparable Gd content. Concerning the bottom electrode materials, the best results in terms of permittivity and leakage currents were achieved with Ru, allowing a capacitance equivalent oxide thickness of similar to 1 nm and a current density of 3 X 10(-8) A/cm(2) at 1 V. Charge storage values up to 60 nC/mm(2) were obtained for mixtures and laminates with thickness below 30 nm. In general, at electric fields below 2-3 MV/cm, normal and trap-compensated Poole-Frenkel conduction mechanisms were competing, whereas at higher fields, Fowler-Nordheim and/or trap-assisted tunneling started to dominate.
The high corrosion resistance of copper is a key feature in the design of copper-lined canisters that will be utilized to protect people and the environment from dangers of spent nuclear fuel far into the future. Our present study sheds light on the effects that sulfide ions in otherwise relatively benign anoxic groundwater may have on the copper of the container material. Using soft X-ray spectroscopy, we have studied the chemistry of the transformation of single-phase copper oxide cover layers (cuprite, tenorite, paratacamite) as well as single-phase oxide powders (paratacamite and malachite) when exposed to aqueous sulfide solutions. While X-ray diffraction shows that the main bulk of the oxides are nearly unaffected, Cu L-edge absorption spectroscopy shows that a cover layer of about 100 nm thickness on the metal substrate is transformed from Cu(II)- to Cu(I)-species. By contrast, paratacamite and malachite powders exposed to the same kind of aqueous sulfide solutions show much less transformation to Cu(I)-species. We conclude that the main mechanism for reduction of Cu(II) on copper is the comproportionation reaction between divalent copper ions from the covering oxide and the underlying metallic copper atoms to form monovalent copper ions. By contrast, the absence of metallic copper inhibits this mechanism in the powders.
This study demonstrates the electrochemical sodiation and desodiation of gallium (Ga). A variety of techniques including galvanostatic cycling, cyclic voltammetry, as well as ex situ and in situ powder X-ray diffraction were used to determine the electrochemical reaction mechanisms. The sodiation and desodiation of Ga occurs reversibly at 0.71 V vs Na+/Na and the sodiated product was determined to be NaGa4 with a theoretical capacity of 96 mAh g(-1) (567 mAh cm(-3)). In addition, an anomalous plateau was observed at 0.66 V vs Na+/Na during the sodiation, which was attributed to a slow diffusion of Na into Ga particles. It was also shown that Na22Ga39 was not formed even if it is one of the expected compounds from the Ga-Na phases diagram. However, new crystalline structures were observed and were attributed to metastable phases of NaGa4.
Spinel LiNi0.5Mn1.5O4 as one of the high-energy positive electrode materials for next generation Li-ion batteries has attracted significant interest due to its economic and environmental advantages. However, the sensitivity of this type of material upon short to long term ambient storage conditions and the impact on the electrochemical performances remains poorly explored. Nevertheless, this remains an important aspect for practical large-scale synthesis, storage and utilization. Herein, we study and compare the evolution of surface chemistry, bulk crystal structure and elemental content evolution and distribution of LiNi0.5Mn1.5O4 using a variety of characterization techniques including XPS and STEM-EDS-EELS, as well as electrochemical analysis. We show that Mn species dominate the outer surface (0–5 nm), while Ni and Li are preferentially located further away and in the bulk. The studied LiNi0.5Mn1.5O4 material is found to be stable, with minor changes in surface or bulk characteristics detected, even after 12 months of storage under ambient air conditions. The low surface reactivity to air also accounts for the minor changes to the electrochemical performance of the air-exposed LiNi0.5Mn1.5O4, compared to the pristine material. This study provides guidance for the appropriate storage, handling and processing of this high-performance cathode material.
Ethylene carbonate (EC) is the archetype solvent in Li-ion batteries. Still, questions remain regarding the numerous possible reaction pathways of EC. Although the reaction pathway involving direct EC reduction and SEI formation is most commonly discussed, EC ring-opening is often observed, but seldomly addressed, especially with respect to SEI formation. By applying Online Electrochemical Mass Spectrometry, the EC ring-opening reaction on carbon is found to start already at similar to 2.5 V vs Li+/Li as initiated by oxygenic carbon surface groups. Later, OH- generated from H2O reduction reaction at similar to 1.6 V further propagates EC to ring-open. The EC reduction reaction occurs <0.9 V but is suppressed depending on the extent of EC ring-opening at higher potentials. Electrode/electrolyte impurities and handling conditions are found to have a significant influence on both processes. In conclusion, SEI formation is shown to be governed by several kinetically competing reaction pathways whereby EC ring-opening can play a significant role.
Polyacrylic acid (PAA) is here studied as a binder material for LiNi0.5Mn1.5O4 (LNMO) cathodes for lithium-ion batteries. When the LNMO electrodes are fabricated with an active mass loading of similar to 10 mg cm-2 (similar to 1.5 mA h cm-2), poor discharge capacity and short cycle life is obtained in full-cells with graphite electrodes. The electrochemical results with PAA are compared with a commonly used water-based binder, sodium carboxymethyl cellulose (CMC), which shows better electrochemical performance. The main cause for these problems in PAA based cells is identified to be the high internal resistance in the initial cycles, caused by factors such as contact resistance, inhomogeneous binder distribution and poor electrolyte wetting of the active material.
Lithium ion batteries (LIB) have become a cornerstone of the shift to electric transportation. In an attempt to decrease the production load and prolong battery life, understanding different degradation mechanisms in state-of-the-art LIBs is essential. Here, we analyze how operational temperature and state-of-charge (SoC) range in cycling influence the ageing of automotive grade 21700 batteries, extracted from a Tesla 3 long Range 2018 battery pack with positive electrode containing LiNixCoyAlzO2 (NCA) and negative electrode containing SiOx-C. In the given study we use a combination of electrochemical and material analysis to understand degradation sources in the cell. Herein we show that loss of lithium inventory is the main degradation mode in the cells, with loss of material on the negative electrode as there is a significant contributor when cycled in the low SoC range. Degradation of NCA dominates at elevated temperatures with combination of cycling to high SoC (beyond 50%).
Alloy electrodes are attracting a lot of interest in the field of Li-ion batteries due to their high energy density. However, they suffer from large volume expansion and contraction during lithiation and delithiation, leading to rapid pulverization and disconnection. A strategy to avoid this is to use self-healing materials. Ga-based liquid alloys have been studied as self-healing electrodes because of their capacity to store Li and their liquid state at room temperature. The so-called "galinstan" (Ga0.77In0.15Sn0.08) exhibits the lowest melting temperatures and has also been used to add self-healing properties in composite electrodes. Nevertheless, its lithiation mechanism and its practical capacity still remain unknown. Also, the reversibility of the lithiation, which is crucial to ensure the self-healing properties offered by the liquid metal, requires investigation. In this work, electrochemical measurements were coupled with XRD and SEM analyses to better understand the redox processes, structural and morphological properties of galinstan as an electrode material in Li-ion batteries. It was shown that only Ga and In would react with Li to form LiGa and LiIn. The reversibility of these reactions and thus the self-healing ability of galinstan was demonstrated through observation of its liquid state before and after electrochemical cycling.
The addition of a compact titanium dioxide (TiO2) layer between the fluorine-doped tin oxide (FTO) coated glass substrate and the mesoporous TiO2 layer in the dye-sensitized solar cell (DSC) based on the iodide/triiodide redox couple (I-/I-3(-)) is known to improve its current-voltage characteristics. The compact layer decreases the recombination of electrons extracted through the FTO layer with I-3(-) around the maximum power point. Furthermore, the short-circuit photocurrent was improved, which previously has been attributed to the improved light transmittance and/or better contact between TiO2 and FTO. Here, we demonstrate that the compact TiO2 layer has another beneficial effect: it blocks the reaction between charge carriers in the FTO and photogenerated diiodide radical species (I-2(-center dot)). Using photomodulated voltammetry, it is demonstrated that the cathodic photocurrent found at bare FTO electrodes is blocked by the addition of a compact TiO2 layer, while the anodic photocurrent due to reaction with I-2(-center dot) is maintained.
Effective diagnostic techniques for Li-ion batteries are vital to ensure that they operate in the required voltage and temperature window to prevent premature degradation and failure. Ultrasonic analysis has been gaining significant attention as a low cost, fast, non-destructive, operando technique for assessing the state-of-charge and state-of-health of Li-ion batteries. Thus far, the majority of studies have focused on a single C-rate at relatively low charge and discharge currents, and as such the relationship between the changing acoustic signal and C-rate is not well understood. In this work, the effect of cell temperature on the acoustic signal is studied and shown to have a strong correlation with the signal's time-of-flight. This correlation allows for the cell temperature to be inferred using ultrasound and to compensate for these effects to accurately predict the state-of-charge regardless of the C-rate at which the cell is being cycled. Ultrasonic state-of-charge monitoring of a cell during a drive cycle illustrates the suitability of this technique to be applied in real-world situations, an important step in the implementation of this technique in battery management systems with the potential to improve pack safety, performance, and efficiency:
Photoelectron spectroscopy (PES) has become an important tool for investigating Li-ion battery materials, in particular for analyzing interfacial structures and reactions. Since the methodology was introduced in the battery research area, PES has undergone a dramatic development regarding photon sources, sample handling and electron energy analyzers. This includes the possibility to use synchrotron radiation with increased intensity and the possibility to vary the photon energy. The aim of the present paper is to describe how PES can be used to investigate battery interfaces and specifically highlight how synchrotron based PES has been implemented to address different questions useful for the development of the Li-ion batteries. We also present some recent developments of the techniques, which have the potential to further push the limits for the use of photoelectron spectroscopy in battery research.
Direct bonding of single crystalline quartz wafers is presented. By this straightforward technique, hermetical seals between quartz wafers can be formed. Nearly Z-cut (the Z-cut rotated 1 degrees 50') and AT-cut wafers bonded spontaneously at room tempera
In the present paper, a complex chemical process involving laser-materials interaction within a strong absorbing gas phase is investigated and characterized. The process utilizes excimer laser pulses to dissociate methylene iodide (CH2I2) in the gas phase and to locally heat the surface of a silicon substrate. These effects induce chemical reactions leading to efficient etching of silicon within the laser-irradiated surface area, in combination with simultaneous deposition of carbon material outside. Because of the sensitive behavior of the photoinduced substrate surface temperature on the absorption conditions in the gas phase, model calculations were performed to improve the design of the system and to analyze the observed experimental results.