Pascal Hartmann

A rechargeable room-temperature sodium superoxide (NaO2) battery

In the search for room-temperature batteries with high energy densities, rechargeable metal-air (more precisely metal-oxygen) batteries are considered as particularly attractive owing to the simplicity of the underlying cell reaction at first glance. Atmospheric oxygen is used to form oxides during discharging, which-ideally-decompose reversibly during charging. Much work has been focused on aprotic Li-O(2) cells (mostly with carbonate-based electrolytes and Li(2)O(2) as a potential discharge product), where large overpotentials are observed and a complex cell chemistry is found. In fact, recent studies evidence that Li-O(2) cells suffer from irreversible electrolyte decomposition during cycling. Here we report on a Na-O(2) cell reversibly discharging/charging at very low overpotentials (< 200 mV) and current densities as high as 0.2 mA cm(-2) using a pure carbon cathode without an added catalyst. Crystalline sodium superoxide (NaO(2)) forms in a one-electron transfer step as a solid discharge product. This work demonstrates that substitution of lithium by sodium may offer an unexpected route towards rechargeable metal-air batteries.

Mesoporous TiO2: Comparison of Classical Sol−Gel and Nanoparticle Based Photoelectrodes for the Water Splitting Reaction

This paper describes a systematic comparison of the photoelectrochemical properties of mesoporous TiO(2) films prepared by the two most prevalent templating methods: The use of preformed, crystalline nanoparticles is generally considered advantageous compared to the usage of molecular precursors such as TiCl(4), since the latter requires a separate heat treatment at elevated temperature to induce crystallization. However, our photoelectrochemical experiments clearly show that sol-gel derived mesoporous TiO(2) films cause an about 10 times higher efficiency for the water splitting reaction than their counterparts obtained from crystalline TiO(2) nanoparticles. This result indicates that for electrochemical applications the performance of nanoparticle-based metal oxide films might suffer from insufficient electronic connectivity.

A comprehensive study on the cell chemistry of the sodium superoxide (NaO2) battery

This work reports on the cell chemistry of a room temperature sodium-oxygen battery using an electrolyte of diethylene glycol dimethyl ether (diglyme) and sodium trifluoromethanesulfonate (NaSO3CF3, sodium triflate). Different from lithium-oxygen cells, where lithium peroxide is found as the discharge product, sodium superoxide (NaO2) is formed in the present cell, with overpotentials as low as 100 mV during charging. Several analytical methods are used to follow the cell reaction during discharge and charge. Changes in structure and morphology are studied by SEM and XRD. It is found that NaO2 grows as cubic particles with feed sizes in the range of 10-50 μm; upon recharge the particles consecutively decompose. Pressure monitoring during galvanostatic cycling shows that the coulombic efficiency (e(-)/O2) for discharge and charge is approx. 1.0, the expected value for NaO2 formation. Also optical spectroscopy is identified as a convenient and useful tool to follow the discharge-charge process. The maximum discharge capacity is found to be limited by oxygen transport within the electrolyte soaked carbon fiber cathode and pore blocking near the oxygen interface is observed. Finally electrolyte decomposition and sodium dendrite growth are identified as possible reasons for the limited capacity retention of the cell. The occurrence of undesired side reactions is analyzed by DEMS measurements during cycling as well as by post mortem XPS investigations.

From lithium to sodium: cell chemistry of room temperature sodium–air and sodium–sulfur batteries

Summary Research devoted to room temperature lithium–sulfur (Li/S8) and lithium–oxygen (Li/O2) batteries has significantly increased over the past ten years. The race to develop such cell systems is mainly motivated by the very high theoretical energy density and the abundance of sulfur and oxygen. The cell chemistry, however, is complex, and progress toward practical device development remains hampered by some fundamental key issues, which are currently being tackled by numerous approaches. Quite surprisingly, not much is known about the analogous sodium-based battery systems, although the already commercialized, high-temperature Na/S8 and Na/NiCl2 batteries suggest that a rechargeable battery based on sodium is feasible on a large scale. Moreover, the natural abundance of sodium is an attractive benefit for the development of batteries based on low cost components. This review provides a summary of the state-of-the-art knowledge on lithium–sulfur and lithium–oxygen batteries and a direct comparison with the analogous sodium systems. The general properties, major benefits and challenges, recent strategies for performance improvements and general guidelines for further development are summarized and critically discussed. In general, the substitution of lithium for sodium has a strong impact on the overall properties of the cell reaction and differences in ion transport, phase stability, electrode potential, energy density, etc. can be thus expected. Whether these differences will benefit a more reversible cell chemistry is still an open question, but some of the first reports on room temperature Na/S8 and Na/O2 cells already show some exciting differences as compared to the established Li/S8 and Li/O2 systems.

Defect chemistry of oxide nanomaterials with high surface area: ordered mesoporous thin films of the oxygen storage catalyst CeO2-ZrO2.

Herein we report the electrical transport properties of a series of ordered mesoporous ceria-zirconia (CexZr1-xO2, referred to as mp-CZO) thin films with both a cubic structure of (17±2) nm diameter pores and nanocrystalline walls. Samples over the whole range of composition, including bare CeO2 and ZrO2, were fabricated by templating strategies using the large diblock copolymer KLE as the structure-directing agent. Both the nanoscale structure and the chemical composition of the mesoporous materials were analyzed by a combination of scanning and transmission electron microscopy, grazing incidence small-angle X-ray scattering, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry. The total conductivity as a function of the film composition, temperature, and oxygen partial pressure was measured using impedance spectroscopy. The mesoporous solid solutions of CeO2-ZrO2 prepared in this work showed a higher stability against thermal ripening than both binary oxides, making them ideal model systems to study both the charge transport properties and the oxygen storage at elevated temperatures. We find that the redox properties of nanocrystalline mp-CZO thin films differ significantly from those of bulk CZO materials reported in the literature and, therefore, propose a defect chemical model of surface regions.

Mesoporous tin-doped indium oxide thin films: effect of mesostructure on electrical conductivity

Abstract We present a versatile method for the preparation of mesoporous tin-doped indium oxide (ITO) thin films via dip-coating. Two poly(isobutylene)-b-poly(ethyleneoxide) (PIB-PEO) copolymers of significantly different molecular weight (denoted as PIB-PEO 3000 and PIB-PEO 20000) are used as templates and are compared with non-templated films to clarify the effect of the template size on the crystallization and, thus, on the electrochemical properties of mesoporous ITO films. Transparent, mesoporous, conductive coatings are obtained after annealing at 500 °C; these coatings have a specific resistance of 0.5 Ω cm at a thickness of about 100 nm. Electrical conductivity is improved by one order of magnitude by annealing under a reducing atmosphere. The two types of PIB-PEO block copolymers create mesopores with in-plane diameters of 20–25 and 35–45 nm, the latter also possessing correspondingly thicker pore walls. Impedance measurements reveal that the conductivity is significantly higher for films prepared with the template generating larger mesopores. Because of the same size of the primary nanoparticles, the enhanced conductivity is attributed to a higher conduction path cross section. Prussian blue was deposited electrochemically within the films, thus confirming the accessibility of their pores and their functionality as electrode material.

Comparison between Na-Ion and Li-Ion Cells: Understanding the Critical Role of the Cathodes Stability and the Anodes Pretreatment on the Cells Behavior

The electrochemical behavior of Na-ion and Li-ion full cells was investigated, using hard carbon as the anode material, and NaNi0.5Mn0.5O2 and LiNi0.5Mn0.5O2 as the cathodes. A detailed description of the structure, phase transition, electrochemical behavior and kinetics of the NaNi0.5Mn0.5O2 cathodes is presented, including interesting comparison with their lithium analogue. The critical effect of the hard carbon anodes pretreatment in the total capacity and stability of full cells is clearly demonstrated. Using impedance spectroscopy in three electrodes cells, we show that the full cell impedance is dominated by the contribution of the cathode side. We discuss possible reasons for capacity fading of these systems, its connection to the cathode structure and relevant surface phenomena.

Interfacial Processes and Influence of Composite Cathode Microstructure Controlling the Performance of All-Solid-State Lithium Batteries

All-solid-state lithium-ion batteries have the potential to become an important class of next-generation electrochemical energy storage devices. However, for achieving competitive performance, a better understanding of the interfacial processes at the electrodes is necessary for optimized electrode compositions to be developed. In this work, the interfacial processes between the solid electrolyte (Li10GeP2S12) and the electrode materials (In/InLi and LixCoO2) are monitored using impedance spectroscopy and galvanostatic cycling, showing a large resistance contribution and kinetic hindrance at the metal anode. The effect of different fractions of the solid electrolyte in the composite cathodes on the rate performance is tested. The results demonstrate the necessity of a carefully designed composite microstructure depending on the desired applications of an all-solid-state battery. While a relatively low mass fraction of solid electrolyte is sufficient for high energy density, a higher fraction of solid electrolyte is required for high power density.

A gamma fluorinated ether as an additive for enhanced oxygen activity in Li–O2 batteries

Perfluorocarbons (PFCs) are known for their high O2 solubility and have been investigated as additives in Li–O2 cells to enhance the cathode performance. However, the immiscibility of PFCs with organic solvents remains the main issue to be addressed as it hinders PFC practical application in Li–O2 cells. Furthermore, the effect of PFC additives on the O2 mass transport properties in the catholyte and their stability has not been thoroughly investigated. In this study, we investigated the properties of 1,1,1,2,2,3,3,4,4-nonafluoro-6-propoxyhexane (TE4), a gamma fluorinated ether, and found it to be miscible with tetraglyme (TEGDME), a solvent commonly used in Li–O2 cells. The results show that with the TE4 additive up to 4 times higher O2 solubility and up to 2 times higher O2 diffusibility can be achieved. With 20 vol% TE4 addition, the discharge capacity increased about 10 times at a high discharge rate of 400 mA gC−1, corresponding to about 0.4 mA cm−2. The chemical stability of TE4 after Li–O2 cell discharge is investigated using 1H and 19F NMR, and the TE4 signal is retained after discharge. FTIR and XPS measurements indicate the presence of Li2O2 as a discharged product, together with side products from the parasitic reactions of LiTFSI salt and TEGDME.

Electrochemical performance of Na0.6[Li0.2Ni0.2Mn0.6]O2 cathodes with high-working average voltage for Na-ion batteries

Na0.6[Li0.2Ni0.2Mn0.6]O2 is synthesized by a self-combustion reaction (SCR) and studied for the first time as a cathode material for Na-ion batteries. The Na0.6[Li0.2Ni0.2Mn0.6]O2 cathode presents remarkable high rate capability and prolonged stability under galvanostatic cycling. A detailed analysis of X-ray diffraction (XRD) patterns at various states of cycling reveals that the excellent structural stability is due to a primarily solid-solution sodiation/desodiation mechanism of the material during cycling. Moreover, a meaningful comparison with Na0.6MnO2 and Na0.6[Li0.2Mn0.8]O2 reveals that the Na0.6[Li0.2Ni0.2Mn0.6]O2 cathode achieves a very high working-average voltage that outperforms most of the lithium-doped manganese-oxide cathodes published to date.