Effects of Iron Species on Low Temperature CO2 Electrolyzers.

Electrochemical energy conversion devices are considered key in reducing CO2 emissions and significant efforts are being applied to accelerate device development. Unlike other technologies, low temperature electrolyzers have the ability to directly convert CO2 into a range of value-added chemicals. To make them commercially viable, however, device efficiency and durability must be increased. Although their design is similar to more mature water electrolyzers and fuel cells, new cell concepts and components are needed. Due to the complexity of the system, singular component optimization is common. As a result, the component interplay is often overlooked. The influence of Fe-species clearly shows that the cell must be considered holistically during optimization, to avoid future issues due to component interference or cross-contamination. Fe-impurities are ubiquitous, and their influence on single components is well-researched. The activity of non-noble anodes has been increased through the deliberate addition of iron. At the same time, however, Fe-species accelerate cathode and membrane degradation. Here, we interpret literature on single components to gain an understanding of how Fe-species influence low temperature CO2 electrolyzers holistically. The role of Fe-species serves to highlight the need for considerations regarding component interplay in general.

An IR Spectroscopy Study of the Degradation of Surface Bound Azido-Groups in High Vacuum.

Controlled surface functionalization with azides to perform on surface "click chemistry" is desired for a large range of fields such as material engineering and biosensors. In this work, the stability of an azido-containing self-assembled monolayer in high vacuum is investigated using in situ Fourier transform infrared spectroscopy. The intensity of the antisymmetric azide stretching vibration is found to decrease over time, suggesting the degradation of the azido-group in high vacuum. The degradation is further investigated at three different temperatures and at seven different nitrogen pressures ranging from 1 × 10-6 mbar to 5 × 10-3 mbar. The degradation is found to increase at higher temperatures and at lower nitrogen pressures. The latter supporting the theory that the degradation reaction involves the decomposition into molecular nitrogen. For the condition with the highest degradation detected, only 63% of azides is found to remain at the surface after 8 h in vacuum. The findings show a significant loss in control of the surface functionalization. The instability of azides in high vacuum should therefore always be considered when depositing or postprocessing azido-containing layers.

Bending impact on the performance of a flexible Li4Ti5O12-based all-solid-state thin-film battery.

The growing demand of flexible electronic devices is increasing the requirements of their power sources. The effect of bending in thin-film batteries is still not well understood. Here, we successfully developed a high active area flexible all-solid-state battery as a model system that consists of thin-film layers of Li4Ti5O12, LiPON, and Lithium deposited on a novel flexible ceramic substrate. A systematic study on the bending state and performance of the battery is presented. The battery withstands bending radii of at least 14 mm achieving 70% of the theoretical capacity. Here, we reveal that convex bending has a positive effect on battery capacity showing an average increase of 5.5%, whereas concave bending decreases the capacity by 4% in contrast with recent studies. We show that the change in capacity upon bending may well be associated to the Li-ion diffusion kinetic change through the electrode when different external forces are applied. Finally, an encapsulation scheme is presented allowing sufficient bending of the device and operation for at least 500 cycles in air. The results are meant to improve the understanding of the phenomena present in thin-film batteries while undergoing bending rather than showing improvements in battery performance and lifetime.

Characterization of thin films of the solid electrolyte Li(x)Mg(1-2x)Al(2+x)O4 (x = 0, 0.05, 0.15, 0.25).

RF-sputtered thin films of spinel Li(x)Mg(1-2x)Al(2+x)O4 were investigated for use as solid electrolyte. The usage of this material can enable the fabrication of a lattice matched battery stack, which is predicted to lead to superior battery performance. Spinel Li(x)Mg(1-2x)Al(2+x)O4 thin films, with stoichiometry (x) ranging between 0 and 0.25, were formed after a crystallization anneal as shown by X-ray diffraction and transmission electron microscopy. The stoichiometry of the films was evaluated by elastic recoil detection and Rutherford backscattering and found to be slightly aluminum rich. The excellent electronic insulation properties were confirmed by both current-voltage measurements as well as by copper plating tests. The electrochemical stability window of the material was probed using cyclic voltammetry. Lithium plating and stripping was observed together with the formation of a Li-Pt alloy, indicating that Li-ions passed through the film. This observation contradicted with impedance measurements at open circuit potential, which showed no apparent Li-ion conductivity of the film. Impedance spectroscopy as a function of potential showed the occurrence of Li-ion intercalation into the Li(x)Mg(1-2x)Al(2+x)O4 layers. When incorporating Li-ions in the material the ionic conductivity can be increased by 3 orders of magnitude. Therefore it is anticipated that the response of Li(x)Mg(1-2x)Al(2+x)O4 is more adequate for a buffer layer than as the solid electrolyte.

Electrochemical deposition of subnanometer Ni films on TiN.

In this paper, we show the electrochemical deposition of a subnanometer film of nickel (Ni) on top of titanium nitride (TiN). We exploit the concept of cluster growth inhibition to enhance the nucleation of new nuclei on the TiN substrate. By deliberately using an unbuffered electrolyte solution, the degree of nucleation is enhanced as growth is inhibited more strongly. This results in a very high particle density and therefore an ultralow coalescence thickness. To prevent the termination of Ni deposition that typically occurs in unbuffered solutions, the concentration of Ni(2+) in solution was increased. We have verified with RBS and ICP-MS that the deposition of Ni on the surface in this case did not terminate. Furthermore, annealing experiments were used to visualize the closed nature of the Ni film. The closure of the deposited film was also confirmed by TOF-SIMS measurements and occurs when the film thickness is still in the subnanometer regime. The ultrathin Ni film was found to be an excellent catalyst for carbon nanotube growth on conductive substrates and can also be applied as a seed layer for bulk deposition of a smooth Ni film on TiN.

First-principles material modeling of solid-state electrolytes with the spinel structure.

Ionic diffusion through the novel (AlxMg1-2xLix)Al2O4 spinel electrolyte is investigated using first-principles calculations, combined with the Kinetic Monte Carlo algorithm. We observe that the ionic diffusion increases with the lithium content x. Furthermore, the structural parameters, formation enthalpies and electronic structures of (AlxMg1-2xLix)Al2O4 are calculated for various stoichiometries. The overall results indicate the (AlxMg1-2xLix)Al2O4 stoichiometries x = 0.2…0.3 as most promising. The (AlxMg1-2xLix)Al2O4 electrolyte is a potential candidate for the all-spinel solid-state battery stack, with the material epitaxially grown between well-known spinel electrodes, such as LiyMn2O4 and Li4+3yTi5O12 (y = 0…1). Due to their identical crystal structure, a good electrolyte-electrode interface is expected.

Tracking Decomposition Layer Formation in Thin-Film Si Electrodes via Thermogalvanic Profiles.

Si anodes are of great interest for next-generation Li-ion batteries due to their exceptional energy density. One of the problems hindering the adoption of this material is the presence of electrolyte decomposition reactions that result in capacity fade and Coulombic inefficiency. This work studies the influence of the decomposition layer in Si on its electrochemical performance using thermogalvanic profiling, a non-destructive in operando technique. This is accomplished by comparing thermogalvanic profiles of uncoated thin-film Si to those of lithium phosphorus oxynitride (LiPON)-coated Si, in which decomposition reactions are inhibited. Through a combination with physico-chemical methods including scanning electron microscopy and time-of-flight secondary ion mass spectrometry, the thermogalvanic profiles are found to contain signatures that reflect the nature of the decomposition layer. More specifically, this decomposition layer appears to gradually develop a passivating function during the first electrochemical cycles. Thermogalvanic profiles collected at later cycles indicate that this passivating behavior is eventually lost, causing the observed capacity degradation. The identification of a passivating regime in Si is highly relevant for the development of high-capacity Li-ion batteries. In addition, the use of thermogalvanic profiles to track the properties of decomposition layers could be of interest for monitoring the formation or degradation of battery cells.

Nano-TiO2/TiN Systems for Electrocatalysis: Mapping the Changes in Energy Band Diagram across the Semiconductor|Current Collector Interface and the Study of Effects of TiO2 Electrochemical Reduction Using UV Photoelectron Spectroscopy.

TiO2 is the most widely used material in photoelectrocatalytic systems. A key parameter to understand its efficacy in such systems is the band bending in the semiconductor layer. In this regard, knowledge on the band energetics at the semiconductor/current collector interface, especially for a nanosemiconductor electrode, is extremely vital as it will directly impact any charge transfer processes at its interface with the electrolyte. Since direct investigation of interfacial electronic features without compromising its structure is difficult, only seldom are attempts made to study the semiconductor/current collector interface specifically. This work utilizes ultraviolet photoelectron spectroscopy (UPS) to determine the valence band maximum (EVBM) and Fermi level (EF) at different depths in a nano-TiO2/TiN thin-film system reached using an Ar gas-clustered ion beam (GCIB). By combining UPS with GCIB depth profiling, we report an innovative approach for truly mapping the energy band structure across a nanosemiconductor/current collector interface. By coupling it with X-ray photoelectron spectroscopy (XPS), correlations among chemistry, chemical bonding, and electronic properties for the nano-TiO2/TiN interface could also be studied. The effects of TiO2 in situ electrochemical reduction in aqueous electrolytes are also investigated where UPS confirmed a decrease in the semiconductor work function (WF) and an associated increase in n-type Ti3+ centers of nano-TiO2 electrodes post use in a 0.2 M potassium chloride solution. We report the use of UPS to precisely determine the energy band diagrams for a nano-TiO2/TiN thin-film interface and confirm the increase in TiO2 n-type dopant concentrations during electrocatalysis, promoting a much more comprehensive and intuitive understanding of the TiO2 activation mechanism by proton intercalation and therefore further optimizing the design process of efficient photocatalytic materials for solar conversion.

Titanium Carboxylate Molecular Layer Deposited Hybrid Films as Protective Coatings for Lithium-Ion Batteries.

The lifetime of lithium-ion batteries can be extended by applying protective coatings to the cathode's surface. Many studies explore atomic layer deposition (ALD) for this purpose. However, the complementary molecular layer deposition (MLD) technique might offer the benefit of depositing hybrid coatings that are flexible and can accommodate potential volume changes of the electrode during charging and discharging of the battery. This study reports the deposition of titanium carboxylate thin films via MLD. The structure and stability of the hybrid films are studied by using Fourier transform IR spectroscopy. The electrochemical properties of two titanium carboxylate films and a "titanicone" MLD film, deposited by using TDMAT and glycerol, are evaluated on top of a TiO2, TiN, and LiMn2O4 electrode. The coatings are found to present good lithium-ion kinetics and to reduce electrolyte decomposition. Overall, the titanium carboxylate films deposited in this work seem promising as protective and elastic coatings for future high-energy lithium-ion battery cathodes.

Measuring the electrical resistivity and contact resistance of vertical carbon nanotube bundles for application as interconnects.

Carbon nanotubes (CNT) are known to be materials with potential for manufacturing sub-20 nm high aspect ratio vertical interconnects in future microchips. In order to be successful with respect to contending against established tungsten or copper based interconnects, though, CNT must fulfil their promise of also providing low electrical resistance in integrated structures using scalable integration processes fully compatible with silicon technology. Hence, carefully engineered growth and integration solutions are required before we can fully exploit their potentialities. This work tackles the problem of optimizing a CNT integration process from the electrical perspective. The technique of measuring the CNT resistance as a function of the CNT length is here extended to CNT integrated in vertical contacts. This allows extracting the linear resistivity and the contact resistance of the CNT, two parameters to our knowledge never reported separately for vertical CNT contacts and which are of utmost importance, as they respectively measure the quality of the CNT and that of their metal contacts. The technique proposed allows electrically distinguishing the impact of each processing step individually on the CNT resistivity and the CNT contact resistance. Hence it constitutes a powerful technique for optimizing the process and developing CNT contacts of superior quality. This can be of relevant technological importance not only for interconnects but also for all those applications that rely on the electrical properties of CNT grown with a catalytic chemical vapor deposition method at low temperature.

Effect of different oxide and hybrid precursors on MOF-CVD of ZIF-8 films.

Chemical vapor deposition of metal-organic frameworks (MOF-CVD) will facilitate the integration of porous and crystalline coatings in electronic devices. In the two-step MOF-CVD process, a precursor layer is first deposited and subsequently converted to a MOF through exposure to linker vapor. We herein report the impact of different metal oxide and metalcone layers as precursors for zeolitic imidazolate framework ZIF-8 films.

Interfacial Conductivity Enhancement and Pore Confinement Conductivity-Lowering Behavior inside the Nanopores of Solid Silica-gel Nanocomposite Electrolytes.

Solid nanocomposite electrolytes (nano-SCEs) that exhibit higher ionic conductivity than the individual confined electrolyte were investigated for high-performance solid-state batteries. Understanding the behavior of Li-ion conduction through the pores is important to design ideal nanoporous structures for nano-SCEs, which are composed of an ionic liquid electrolyte (ILE) in a highly porous (∼90%) silica matrix. To establish the relationship between the pore structure of the silica matrix and the ionic conductivity of the solid nanocomposite, the liquid electrolyte fraction was successfully extracted from the nano-SCE to reveal the fragile porous silica matrix. A careful drying using the CO2 supercritical drying method helps in sustaining the original structure, preventing its collapse due to surface tension. The pore size distribution, Brunauer-Emmett-Teller (BET) surface area, and porosity were characterized using scanning electron microscopy, transmission electron microscopy, and N2 adsorption/desorption techniques. Our results revealed a wide size distribution of macropores and mesopores in the silica matrix. The pore size increased and the effective surface area decreased with increasing ILE/SiO2 molar ratio. The interface conductivity enhancement was found to increase with the thickness of the adsorbed (ice-like) bound-water layer on the silica surface, confirming that the strong hydrogen bonding of the adsorbed ionic liquid molecules on the bound-water layer causes the conduction promotion effect in the nano-SCE. In addition, a large number of small pores lead to a severe pore confinement effect that results in a decreased conductivity due to the increasing viscosity of the ILE filling the pores. The conductivity can be improved by realizing a nano-SCE with an optimized pore size to minimize the pore confinement effect.

Growth and characterization of horizontally suspended CNTs across TiN electrode gaps.

A technique is proposed to grow horizontal carbon nanotubes (CNTs) bridging metal electrodes and to assess their electrical properties. A test structure was utilized that allows for selective electrochemical sidewall catalyst placement. The selectivity of the technique is based on the connection of the desired metal electrodes to the silicon substrate where the potential for electrochemical deposition was applied. Control over the Ni catalyst size (15-30 nm) and density (up to 3 x 10(11) particles cm(-2)) is demonstrated. Horizontal CNTs with controlled diameter and density were obtained by CVD growth perpendicular to the sidewalls of patterned TiN electrode structures. Electrode gaps with spacings from 200 nm up to 5 microm could be bridged by both direct CNT-electrode contact and CNT-CNT entanglement. The TiN-CNT-TiN and TiN-CNT-CNT-TiN bridges were electrically characterized without any further post-growth contacting. Resistance values as low as 40 Omega were measured for the smallest gap spacing and depended mainly on the number and configuration of the CNT bridges. The proposed method could be implemented for CNT-based horizontal interconnections and be a route to make different nanoelectronic devices such as chemical and electromechanical sensors.

Silica gel solid nanocomposite electrolytes with interfacial conductivity promotion exceeding the bulk Li-ion conductivity of the ionic liquid electrolyte filler.

The transition to solid-state Li-ion batteries will enable progress toward energy densities of 1000 W·hour/liter and beyond. Composites of a mesoporous oxide matrix filled with nonvolatile ionic liquid electrolyte fillers have been explored as a solid electrolyte option. However, the simple confinement of electrolyte solutions inside nanometer-sized pores leads to lower ion conductivity as viscosity increases. Here, we demonstrate that the Li-ion conductivity of nanocomposites consisting of a mesoporous silica monolith with an ionic liquid electrolyte filler can be several times higher than that of the pure ionic liquid electrolyte through the introduction of an interfacial ice layer. Strong adsorption and ordering of the ionic liquid molecules render them immobile and solid-like as for the interfacial ice layer itself. The dipole over the adsorbate mesophase layer results in solvation of the Li+ ions for enhanced conduction. The demonstrated principle of ion conduction enhancement can be applied to different ion systems.

A High-Surface-Area Carbon-Coated 3D Nickel Nanomesh for Li-O2 Batteries.

Nanostructured electrodes show great promises for application in batteries and could improve their energy and power density. Herein, a carbon-coated 3D Ni nanomesh was used as an air cathode for non-aqueous Li-air (O2 ) battery applications. A 3 µm thick 3D Ni nanomesh was fabricated, showing an excellent surface area/footprint area ratio (90 cm2 :1 cm2 ) and uniformly distributed pores, on which a conformal amorphous carbon coating was applied for the first time. This carbon-coated 3D Ni nanomesh showed an approximately 100 times larger charge-footprint capacity than that of the glassy carbon electrode. Owing to its tunable properties, a capacity higher than 6 mAh cm-2 could be achieved for a carbon-coated 3D Ni nanomesh with a thickness of 100 µm, whereas the practical capacities of current air electrodes are in the range of 2 mAh cm-2 .

Combining High Porosity with High Surface Area in Flexible Interconnected Nanowire Meshes for Hydrogen Generation and Beyond.

Nanostructured metals with large surface area have a great potential for multiple device applications. Although various metal architectures based on metal nanoligaments and nanowires are well known, they typically show a tradeoff between mechanical robustness, high surface area, and high (macro)porosity, which, when combined, could significantly improve the performance of devices such as batteries, electrolyzers, or sensors. In this work, we rationally designed templated networks of interconnected metal nanowires, combining for the first time high porosity of metal foams, narrowly distributed macropores, and a very high surface area of nanoporous dealloyed metals. Thanks to their structural uniformity, the few-micron thick nanowire meshes are also remarkably flexible and durable. We show how the textural properties of the material can be precisely tuned to optimize the nanowire networks for applications in different devices. In an exemplary application in electrolytic production of hydrogen, thanks to its high surface area, a few-micron thick nanomesh outperformed a 300 times thicker nickel foam. Furthermore, thanks to its high porosity, the Pt-doped nanomesh surpassed a microporous Pt/C cloth, demonstrating benefits of the optimally designed nanowire structure for a simultaneous improvement and miniaturization of electrochemical devices. This work extends the potential of interconnected nanowires to multiple new research and industrial applications requiring highly porous and flexible conductive materials with a high surface-to-volume ratio.

The transformation behaviour of "alucones", deposited by molecular layer deposition, in nanoporous Al2O3 layers.

Nanoporous alumina films can be synthesized from hybrid organic-inorganic "alucone" films deposited by molecular layer deposition (MLD) by wet etching in deionized water or calcination in air at 500 °C. This transformation process was systematically investigated for two alucone chemistries based on ethylene glycol (EG) and glycerol (GL). Ellipsometric porosimetry (EP) was used for the characterization of the porous alumina structures that are formed as a result of the treatments. Etching in deionized water transforms both EG- and GL-alucones into porous alumina with a porosity of about 40%, albeit with a different pore structure: cylindrical pores for EG-alucones and ink-bottle structures for GL-alucones. Calcination in air up to 500 °C only successfully transformed EG-alucones into porous alumina if the chosen heating and cooling rate was lower than 200 °C h-1. Below this ramp rate, a relationship between the resulting porosity and the ramp rate was found. At the lowest investigated ramp rate of 20 °C h-1, the highest porosity of 36% was achieved. For this treatment type, the pore shape was of the ink-bottle type for all investigated ramp rates with narrow 1 nm-sized pores. Infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy revealed that the final chemistry of the porous structures was slightly different for both treatments due to trace amounts of carbon left behind by water etching. This suggests that the internal surface of the porous structure has a different termination depending on the chosen treatment. The precise thickness control and conformal nature inherent to MLD combined with the wet and heat treatments enables the coating of complex 3D structures with a porous alumina film with a well-defined thickness and pore structure.

Nanoscale electrochemical response of lithium-ion cathodes: a combined study using C-AFM and SIMS.

The continuous demand for improved performance in energy storage is driving the evolution of Li-ion battery technology toward emerging battery architectures such as 3D all-solid-state microbatteries (ASB). Being based on solid-state ionic processes in thin films, these new energy storage devices require adequate materials analysis techniques to study ionic and electronic phenomena. This is key to facilitate their commercial introduction. For example, in the case of cathode materials, structural, electrical and chemical information must be probed at the nanoscale and in the same area, to identify the ionic processes occurring inside each individual layer and understand the impact on the entire battery cell. In this work, we pursue this objective by using two well established nanoscale analysis techniques namely conductive atomic force microscopy (C-AFM) and secondary ion mass spectrometry (SIMS). We present a platform to study Li-ion composites with nanometer resolution that allows one to sense a multitude of key characteristics including structural, electrical and chemical information. First, we demonstrate the capability of a biased AFM tip to perform field-induced ionic migration in thin (cathode) films and its diagnosis through the observation of the local resistance change. The latter is ascribed to the internal rearrangement of Li-ions under the effect of a strong and localized electric field. Second, the combination of C-AFM and SIMS is used to correlate electrical conductivity and local chemistry in different cathodes for application in ASB. Finally, a promising starting point towards quantitative electrochemical information starting from C-AFM is indicated.

Electrolytic Manganese Dioxide Coatings on High Aspect Ratio Micro-Pillar Arrays for 3D Thin Film Lithium Ion Batteries.

In this work, we present the electrochemical deposition of manganese dioxide (MnO2) thin films on carbon-coated TiN/Si micro-pillars. The carbon buffer layer, grown by plasma enhanced chemical vapor deposition (PECVD), is used as a protective coating for the underlying TiN current collector from oxidation, during the film deposition, while improving the electrical conductivity of the stack. A conformal electrolytic MnO2 (EMD) coating is successfully achieved on high aspect ratio C/TiN/Si pillar arrays by tailoring the deposition process. Lithiation/Delithiation cycling tests have been performed. Reversible insertion and extraction of Li⁺ through EMD structure are observed. The fabricated stack is thus considered as a good candidate not only for 3D micorbatteries but also for other energy storage applications.

Electrical Characterization of Ultrathin RF-Sputtered LiPON Layers for Nanoscale Batteries.

Ultrathin lithium phosphorus oxynitride glass (LiPON) films with thicknesses down to 15 nm, deposited by reactive sputtering in nitrogen plasma, were found to be electronically insulating. Such ultrathin electrolyte layers could lead to high power outputs and increased battery energy densities. The effects of stoichiometry, film thickness, and substrate material on the ionic conductivity were investigated. As the amount of nitrogen in the layers increased, the activation energy of the ionic conductivity decreased from 0.63 to 0.53 eV, leading to a maximum conductivity of 1 × 10(-6) S/cm. No dependence of the ionic conductivity on the film thickness or substrate material could be established. A detailed analysis of the equivalent circuit model used to fit the impedance data is provided. Polarization measurements were performed to determine the electronic leakage in these ultrathin films. A 15-nm LiPON layer on a TiN substrate showed electronically insulating properties with electronic resistivity values around 10(15) Ω·cm. To our knowledge, this is the thinnest RF-sputtered LiPON layer shown to be electronically insulating while retaining good ionic conductivity.