Spatiotemporal Quantification of Lithium both in Electrode and in Electrolyte with Atomic Precision via Operando Neutron Absorption.

The commercial uptake of lithium-sulfur (Li-S) batteries is undermined by their rapid performance decay and short cycle life. These problems originate from the dissolution of lithium polysulfide in liquid electrolytes, causing charge and active material to shuttle between electrodes. The dynamics of intractable polysulfide migration at different length scales often tend to escape the probing ability of many analytical techniques. Spatial and temporal visualization of Li in Li-S electrodes and direct mechanistic understanding of how polysulfides are regulated across Li-S batteries starting from current collector and active layer coating to electrode-electrolyte interface are still lacking. To address this we employ neutron depth profiling across Li-S electrodes using the naturally occurring isotope, 6Li, which yields direct spatial information on Li-S electrochemistry. Using three types of Li-S electrodes, namely, carbon-sulfur, carbon-sulfur with 10% lithium titanium oxide (LTO), and carbon-sulfur with LTO membrane, we provide direct evidence for the migration, adsorption, and confinement of polysulfides in Li-S cells at work. Our findings further provide insights into the dynamics of polysulfide dissolution and re-utilization in relation to Li-S battery capacity and longevity to aid rational electrode designs toward high-energy, safe, and low-cost batteries.

Properties and promises of nanosized insertion materials for Li-ion batteries.

The substantial influence of crystallite size on the properties of Li-ion storage materials has spurred intensive research in the emerging area of nanoionics. The development of nanoscale storage materials offers a promising strategy to increase the energy storage capabilities of Li-ion batteries, potentially making them suitable for electric vehicles. Nanosizing, which increases surface area, enhances the importance of interfaces and surfaces on directly observable materials properties such as the voltage profile and the phase diagram. As a result, nanosized materials can show improved storage properties, and materials inactive at the micro size can become excellent storage materials. We suggest novel surface storage mechanisms to explain these phenomena. First-order phase transitions, which are responsible for the batteries' constant voltage output, are partially suppressed at the nanoscale. So far the morphological changes during the phase transition remain unclear. A complete understanding of the equilibrium and non-equilibrium properties of a collection of nanosized electrode particles within an actual electrode remains a formidable challenge. In this Account, we describe the efforts toward understanding the effects of nanosizing and its applications in representative insertion materials. We are particularly interested in the mechanisms and properties that will help to increase the energy storage of Li-ion batteries. We review and discuss the nanosize properties of lithium insertion materials, olivine LiFePO4, and titanium oxides. Although nanosizing intrinsically destabilizes materials, which is potentially detrimental for battery performance, the relative stability of oxide and phosphate insertion compounds makes it possible to exploit the advantages of nanosizing in these materials. The larger capacities and typical voltage profiles in nanosized materials appear to be related to the surface and interface properties that become pronounced at the nanosize, providing a potential means of tailoring the material properties by particle size and shape. The large irreversible capacity at the surface of some materials such as titanium oxides represents a disadvantage of nanosizing, but research is suggesting ways to resolve this problem. The changes in the first-order phase transition upon (de)lithiation could be related to the interface between the coexisting phases. At these interfaces, concentration gradients and strain lead to energy penalties, which significantly influence the thermodynamics of nanomaterial grains. However, it is less clear what nanoscaling effects predominate in the large collection of particles in actual electrodes. The complexity of these materials at the nanoscale and the difficulty in observing them in situ pose additional challenges. Future demands for stored electricity will require significant research progress in both nanomaterials synthesis and in situ monitoring.

Electronic and vibronic properties of a discotic liquid-crystal and its charge transfer complex.

Discotic liquid crystalline (DLC) charge transfer (CT) complexes combine visible light absorption and rapid charge transfer characteristics, being favorable properties for photovoltaic (PV) applications. We present a detailed study of the electronic and vibrational properties of the prototypic 1:1 mixture of discotic 2,3,6,7,10,11-hexakishexyloxytriphenylene (HAT6) and 2,4,7-trinitro-9-fluorenone (TNF). It is shown that intermolecular charge transfer occurs in the ground state of the complex: a charge delocalization of about 10(-2) electron from the HAT6 core to TNF is deduced from both Raman and our previous NMR measurements [L. A. Haverkate, M. Zbiri, M. R. Johnson, B. Deme, H. J. M. de Groot, F. Lefeber, A. Kotlewski, S. J. Picken, F. M. Mulder, and G. J. Kearley, J. Phys. Chem. B 116, 13098 (2012)], implying the presence of permanent dipoles at the donor-acceptor interface. A combined analysis of density functional theory calculations, resonant Raman and UV-VIS absorption measurements indicate that fast relaxation occurs in the UV region due to intramolecular vibronic coupling of HAT6 quinoidal modes with lower lying electronic states. Relatively slower relaxation in the visible region the excited CT-band of the complex is also indicated, which likely involves motions of the TNF nitro groups. The fast quinoidal relaxation process in the hot UV band of HAT6 relates to pseudo-Jahn-Teller interactions in a single benzene unit, suggesting that the underlying vibronic coupling mechanism can be generic for polyaromatic hydrocarbons. Both the presence of ground state CT dipoles and relatively slow relaxation processes in the excited CT band can be relevant concerning the design of DLC based organic PV systems.

Reduced enthalpy of metal hydride formation for Mg-Ti nanocomposites produced by spark discharge generation.

Spark discharge generation was used to synthesize Mg-Ti nanocomposites consisting primarily of a metastable body-centered-cubic (bcc) alloy of Mg and Ti. The bcc Mg-Ti alloy transformed upon hydrogenation into the face-centered-cubic fluorite Mg1-yTiyHx phase with favorable hydrogen storage properties. Both metal and metal hydride nanocomposites showed a fractal-like porous morphology, with a primary particle size of 10-20 nm. The metal content of 70 atom % (at %) Mg and 30 at % Ti, consistently determined by XRD, TEM-EDS, and ICP-OES, was distributed uniformly across the as-prepared sample. Pressure-composition isotherms for the Mg-Ti-H nanocomposites revealed large differences in the thermodynamics relative to bulk MgH2, with a much less negative enthalpy of formation of the hydride as small as -45 ± 3 kJ/molH2 as deduced from van't Hoff plots. The plateau pressures of hydrogenation were substantially higher than those for bulk MgH2 in the low temperature range from 150 to 250 °C. The reaction entropy was simultaneously reduced to values down to 84 ± 5 J/K mol H2, following a linear relationship between the enthalpy and entropy. Plausible mechanisms for the modified thermodynamics are discussed, including the effect of lattice strains, the presence of interfaces and hydrogen vacancies, and the formation of excess free volume due to local deformations. These mechanisms all rely on the finely interdispersed nanocomposite character of the samples which is maintained by grain refinement.

Effect of Temperature and H Flux on the NH3 Synthesis via Electrochemical Hydrogen Permeation.

Invited for this month's cover is the group of Prof. Fokko M. Mulder at the Delft University of Technology. The image on the cover shows how in the NH3 synthesis via hydrogen-permeable electrode the N, H species on the catalyst surface can be controlled, using the analogy of a traffic controller. The Research Article itself is available at 10.1002/cssc.202300460.

Effect of Temperature and H Flux on the NH3 Synthesis via Electrochemical Hydrogen Permeation.

Ammonia is an indispensable commodity and a potential carbon free energy carrier. The use of H permeable electrodes to synthesize ammonia from N2 , water and electricity, provides a promising alternative to the fossil fuel based Haber-Bosch process. Here, H permeable Ni electrodes are investigated in the operating temperature range 25-120 °C, and varying the rate of electrochemical atomic hydrogen permeation. At 120 °C, a steady reaction is achieved for over 12 h with 10 times higher cumulative NH3 production and almost 40-fold increase in faradaic efficiency compared to room temperature experiments. NH3 is formed with a cell potential of 1.4 V, corresponding to a minimum electrical energy investment of 6.6 kWh kg-1 NH 3 ${{_{{\rm NH}{_{3}}}}}$ . The stable operation is attributed to a balanced control over the population of N, NHx and H species at the catalyst surface. These findings extend the understanding on the mechanisms involved in the nitrogen reduction reaction and may facilitate the development of an efficient green ammonia synthesis process.

Revisiting the Electrochemical Nitrogen Reduction on Molybdenum and Iron Carbides: Promising Catalysts or False Positives?

The electrochemical dinitrogen reduction reaction (NRR) has recently gained much interest as it can potentially produce ammonia from renewable intermittent electricity and replace the Haber-Bosch process. Previous literature studies report Fe- and Mo-carbides as promising electrocatalysts for the NRR with activities higher than other metals. However, recent understanding of extraneous ammonia and nitrogen oxide contaminations have challenged previously published results. Here, we critically assess the NRR performance of several Fe- and Mo-carbides reported as promising by implementing a strict experimental protocol to minimize the effect of impurities. The successful synthesis of α-Mo2C decorated carbon nanosheets, α-Mo2C nanoparticles, θ-Fe3C nanoparticles, and χ-Fe5C2 nanoparticles was confirmed by X-ray diffraction, scanning and transmission electron microscopy, and X-ray photoelectron and Mössbauer spectroscopy. After performing NRR chronoamperometric tests with the synthesized materials, the ammonia concentrations varied between 37 and 124 ppb and are in close proximity with the estimated ammonia background level. Notwithstanding the impracticality of these extremely low ammonia yields, the observed ammonia did not originate from the electrochemical nitrogen reduction but from unavoidable extraneous ammonia and NO x impurities. These findings are in contradiction with earlier literature studies and show that these carbide materials are not active for the NRR under the employed conditions. This further emphasizes the importance of a strict protocol in order to distinguish between a promising NRR catalyst and a false positive.

Operando isotope selective ammonia quantification in nitrogen reduction studies via gas chromatography-mass spectrometry.

Rapid advances in electrocatalytic ammonia synthesis are impeded by laborious detection methods commonly used in the field and by constant risk of external contaminations, which generates misleading false positives. We developed a facile real-time GC-MS method for sensitive isotope NH3 quantification, requiring no external sample manipulations. This method ensures high detection reliability paramount to accelerate (electro-)catalyst screening.

Overcoming Nitrogen Reduction to Ammonia Detection Challenges: The Case for Leapfrogging to Gas Diffusion Electrode Platforms.

The nitrogen reduction reaction (NRR) is a promising pathway toward the decarbonization of ammonia (NH3) production. However, unless practical challenges related to the detection of NH3 are removed, confidence in published data and experimental throughput will remain low for experiments in aqueous electrolyte. In this perspective, we analyze these challenges from a system and instrumentation perspective. Through our analysis we show that detection challenges can be strongly reduced by switching from an H-cell to a gas diffusion electrode (GDE) cell design as a catalyst testing platform. Specifically, a GDE cell design is anticipated to allow for a reduction in the cost of crucial 15N2 control experiments from €100-2000 to less than €10. A major driver is the possibility to reduce the 15N2 flow rate to less than 1 mL/min, which is prohibited by an inevitable drop in mass-transport at low flow rates in H-cells. Higher active surface areas and improved mass transport can further circumvent losses of NRR selectivity to competing reactions. Additionally, obstacles often encountered when trying to transfer activity and selectivity data recorded at low current density in H-cells to commercial device level can be avoided by testing catalysts under conditions close to those in commercial devices from the start.

In Situ Study of Hydrogen Permeable Electrodes for Electrolytic Ammonia Synthesis Using Near Ambient Pressure XPS.

Hydrogen permeable electrodes can be utilized for electrolytic ammonia synthesis from dinitrogen, water, and renewable electricity under ambient conditions, providing a promising route toward sustainable ammonia. The understanding of the interactions of adsorbing N and permeating H at the catalytic interface is a critical step toward the optimization of this NH3 synthesis process. In this study, we conducted a unique in situ near ambient pressure X-ray photoelectron spectroscopy experiment to investigate the solid-gas interface of a Ni hydrogen permeable electrode under conditions relevant for ammonia synthesis. Here, we show that the formation of a Ni oxide surface layer blocks the chemisorption of gaseous dinitrogen. However, the Ni 2p and O 1s XPS spectra reveal that electrochemically driven permeating atomic hydrogen effectively reduces the Ni surface at ambient temperature, while H2 does not. Nitrogen gas chemisorbs on the generated metallic sites, followed by hydrogenation via permeating H, as adsorbed N and NH3 are found on the Ni surface. Our findings suggest that the first hydrogenation step to NH and the NH3 desorption might be limiting under the operating conditions. The study was then extended to Fe and Ru surfaces. The formation of surface oxide and nitride species on iron blocks the H permeation and prevents the reaction to advance; while on ruthenium, the stronger Ru-N bond might favor the recombination of permeating hydrogen to H2 over the hydrogenation of adsorbed nitrogen. This work provides insightful results to aid the rational design of efficient electrolytic NH3 synthesis processes based on but not limited to hydrogen permeable electrodes.

Dynamic solubility limits in nanosized olivine LiFePO4.

Because of its stability, nanosized olivine LiFePO(4) opens the door toward high-power Li-ion battery technology for large-scale applications as required for plug-in hybrid vehicles. Here, we reveal that the thermodynamics of first-order phase transitions in nanoinsertion materials is distinctly different from bulk materials as demonstrated by the decreasing miscibility gap that appears to be strongly dependent on the overall composition in LiFePO(4). In contrast to our common thermodynamic knowledge, that dictates solubility limits to be independent of the overall composition, combined neutron and X-ray diffraction reveals strongly varying solubility limits below particle sizes of 35 nm. A rationale is found based on modeling of the diffuse interface. Size confinement of the lithium concentration gradient, which exists at the phase boundary, competes with the in bulk energetically favorable compositions. Consequently, temperature and size diagrams of nanomaterials require complete reconsideration, being strongly dependent on the overall composition. This is vital knowledge for the future nanoarchitecturing of superior energy storage devices as the performance will heavily depend on the disclosed nanoionic properties.

Equilibrium lithium-ion transport between nanocrystalline lithium-inserted anatase TiO2 and the electrolyte.

The power density of lithium-ion batteries requires the fast transfer of ions between the electrode and electrolyte. The achievable power density is directly related to the spontaneous equilibrium exchange of charged lithium ions across the electrolyte/electrode interface. Direct and unique characterization of this charge-transfer process is very difficult if not impossible, and consequently little is known about the solid/liquid ion transfer in lithium-ion-battery materials. Herein we report the direct observation by solid-state NMR spectroscopy of continuous lithium-ion exchange between the promising nanosized anatase TiO(2) electrode material and the electrolyte. Our results reveal that the energy barrier to charge transfer across the electrode/electrolyte interface is equal to or greater than the barrier to lithium-ion diffusion through the solid anatase matrix. The composition of the electrolyte and in turn the solid/electrolyte interface (SEI) has a significant effect on the electrolyte/electrode lithium-ion exchange; this suggests potential improvements in the power of batteries by optimizing the electrolyte composition.

Accelerating 1H NMR Detection of Aqueous Ammonia.

Direct electrolytic N2 reduction to ammonia (NH3) is a renewable alternative to the Haber-Bosch process. The activity and selectivity of electrocatalysts are evaluated by measuring the amount of NH3 in the electrolyte. Quantitative 1H nuclear magnetic resonance (qNMR) detection reduces the bench time to analyze samples of NH3 (present in the assay as NH4 +) compared to conventional spectrophotometric methods. However, many groups do not have access to an NMR spectrometer with sufficiently high sensitivity. We report that by adding 1 mM paramagnetic Gd3+ ions to the NMR sample, the required analysis time can be reduced by an order of magnitude such that fast NH4 + detection becomes accessible with a standard NMR spectrometer. Accurate, internally calibrated quantification is possible over a wide pH range.

Ammonia Synthesis at Ambient Conditions via Electrochemical Atomic Hydrogen Permeation.

Direct electrochemical nitrogen reduction holds the promise of enabling the production of carbon emission-free ammonia, which is an important intermediate in the fertilizer industry and a potential green energy carrier. Here we show a strategy for ambient condition ammonia synthesis using a hydrogen permeable nickel membrane/electrode that spatially separates the electrolyte and hydrogen reduction side from the dinitrogen activation and hydrogenation sites. Gaseous ammonia is produced catalytically in the absence of electrolyte via hydrogenation of adsorbed nitrogen by electrochemically permeating atomic hydrogen from water reduction. Dinitrogen activation at the polycrystalline nickel surface is confirmed with 15N2 isotope labeling experiments, and it is attributed to a Mars-van Krevelen mechanism enabled by the formation of N-vacancies upon hydrogenation of surface nitrides. We further show that gaseous hydrogen does not hydrogenate the adsorbed nitrogen, strengthening the benefit of having an atomic hydrogen permeable electrode. The proposed approach opens new directions toward green ammonia.

Neutron Diffraction Study of a Sintered Iron Electrode In Operando.

Iron is a promising, earth-abundant material for future energy applications. In this study, we use a neutron diffractometer to investigate the properties of an iron electrode in an alkaline environment. As neutrons penetrate deeply into materials, neutron scattering gives us a unique insight into what is happening inside the electrode. We made our measurements while the electrode was charging or discharging. Our key questions are: Which phases occur for the first and second discharge plateaus? And why are iron electrodes less responsive at higher discharge rates? We conclude that metallic iron and iron hydroxide form the redox pair for the first discharge plateau. For the second discharge plateau, we found a phase similar to feroxyhyte but with symmetrical and equally spaced arrangement of hydrogen atoms. The data suggest that no other iron oxide or iron (oxy)hydroxide formed. Remarkable findings include the following: (1) substantial amounts of iron hydroxide are always present inside the electrode. (2) Passivation is mostly caused by iron hydroxide that is unable to recharge. (3) Iron fractions change as expected, while iron hydroxide fractions are delayed, resulting in substantial amounts of amorphous, undetectable iron phases. About 40% of the participating iron of the first plateau and about 55% of the participating iron for the second plateau are undetectable. (4) Massive and unexpected precipitation of iron hydroxide occurs in the transition from discharging to charging. (2), (3), and (4) together cause accumulation of iron hydroxide inside the electrode.

Li-ion diffusion in the equilibrium nanomorphology of spinel Li(4+x)Ti(5)O(12).

Li(4)Ti(5)O(12) spinel as Li-ion electrode material combines good capacity, excellent cycleability with a high rate capability. Although the potential of about 1.56 V vs Li is relatively high, these features make it the anode of choice for state of the art high power Li-ion batteries. Although the flat voltage profile reflects a two-phase reaction during lithiation, the small change in lattice parameters upon lithiation ("zero-strain" property) leads to a solid solution in equilibrium, as recently demonstrated with diffraction. In this study, the morphology and Li-ion mobility is studied by NMR spectroscopy leading to a more detailed picture, showing that the solid solution in Li(4+x)Ti(5)O(12) spinel should actually be described as domains with sizes less than 9 nm having either tetrahedral (8a) Li occupation or octahedral (16c) Li occupation. The abundant domain boundaries and the associated disorder appear to be responsible for the facile diffusion through the lattice, and hence these nm-sized domains are most likely the origin of the relative high rate capability of this material as electrode for Li-ion batteries. The small domain size, smaller than typical Debye lengths, makes that the material electrochemically behaves as a solid solution. As such, the results give insight in the fundamental properties of the "zero-strain" Li(4)Ti(5)O(12) spinel material explaining the favorable Li-ion battery electrode properties on an atomic level.

Hydrogen in porous tetrahydrofuran clathrate hydrate.

The lack of practical methods for hydrogen storage is still a major bottleneck in the realization of an energy economy based on hydrogen as energy carrier.1 Storage within solid-state clathrate hydrates,2-4 and in the clathrate hydrate of tetrahydrofuran (THF), has been recently reported.5, 6 In the latter case, stabilization by THF is claimed to reduce the operation pressure by several orders of magnitude close to room temperature. Here, we apply in situ neutron diffraction to show that-in contrast to previous reports([5, 6])-hydrogen (deuterium) occupies the small cages of the clathrate hydrate only to 30 % (at 274 K and 90.5 bar). Such a D(2) load is equivalent to 0.27 wt. % of stored H(2). In addition, we show that a surplus of D(2)O results in the formation of additional D(2)O ice Ih instead of in the production of sub-stoichiometric clathrate that is stabilized by loaded hydrogen (as was reported in ref. 6). Structure-refinement studies show that [D(8)]THF is dynamically disordered, while it fills each of the large cages of [D(8)]THF17D(2)O stoichiometrically. Our results show that the clathrate hydrate takes up hydrogen rapidly at pressures between 60 and 90 bar (at about 270 K). At temperatures above approximately 220 K, the H-storage characteristics of the clathrate hydrate have similarities with those of surface-adsorption materials, such as nanoporous zeolites and metal-organic frameworks,7, 8 but at lower temperatures, the adsorption rates slow down because of reduced D(2) diffusion between the small cages.

Direct observation of space charge induced hydrogen ion insertion in nanoscale anatase TiO2.

Space charge induced 2H+ densities up to 2H+ (0.17)TiO2 are observed directly using neutron diffraction on two different nanoscale particle sizes of anatase TiO2 immersed in sulfuric acid, and consistent with experimental evidence modelling shows that these ions show rapid self diffusion.