A nitroxide-containing cathode material for organic radical batteries studied with pulsed EPR spectroscopy

An electron spin echo in a nitroxide-containing polymer cathode film for organic radical batteries is observed for various states of charge at cryogenic temperatures. The EPR-detected state of charge (ESOC), as inferred from the number of paramagnetic centers in the film, is compared to the results of Coulomb counting based on galvanostatic charging. Spin concentration, longitudinal relaxation times T(1 )and phase memory times T-m strongly correlate with the ESOC. In the discharged film, the spin concentration reaches 5 +/- 3x10(20) cm(-3), causing a phase memory time T-m << 100 ns (shorter than the resonator ring-down time) that hinders the detection of the spin echo. In the charged film, the decreased spin concentration results in a longer T-m between 100 ns and 300 ns that enables spin-echo detection, yet limits the length of the microwave pulse sequence. The short, broad-band pulses cause instantaneous diffusion in the unoxidized domains across the oxidized film, affecting the relative peak intensities in the pulsed EPR spectrum. By simulating the spectral distortion caused by instantaneous diffusion, we obtain information on the local spin concentration, which complements the information on the 'bulk' spin concentration determined by electrochemistry and continuous-wave EPR spectroscopy

a [Ni(Salen)]‐TEMPO redox‐conducting polymer for organic batteries

Redox-active nitroxyl-containing polymers are promising candidates as possible replacements for inorganic based energy-storage materials, due to their high energy density and fast redox kinetics. One challenge towards the implementation of such a system is the insufficient electrical conductivity, impeding the charge collection even with highly conductive additives. Herein, the first implementation of a polymeric bis(salicylideniminato) nickel (NiSalen) conductive backbone as an active charge-collecting wire is reported. NiSalen simultaneously serves as a charge collector for nitroxyl pendants and supports the redox capacity of the material. This novel polymer exhibits a specific capacity of up to 91.5 mAh g−1, retaining 87 % of its theoretical capacity at 800 C and more than 30 % at as high as 3000 C (66 % capacity retention after 2000 cycles). The properties of the new material upon operation was studied by means of operando electrochemical methods, UV-Vis, and electron paramagnetic resonance spectroscopy

Spins at work: probing charging and discharging of organic radical batteries by electron paramagnetic resonance spectroscopy

Organic radical batteries (ORBs) are a promising class of electrochemical power sources employing organic radicals as redox-active groups. This article reports on the development of a versatile on-substrate electrode setup for spectroelectrochemical Electron Paramagnetic Resonance (EPR) measurements on redox conductive polymers for ORBs. Quantitative in operando EPR experiments performed on electrochemical cells with a di-TEMPO Ni-Salen polymer as active electrode material demonstrate a strong decrease in the number of paramagnetic centers upon oxidizing the film. The distinct EPR signatures of the TEMPO-containing polymer and its fragments in different molecular environments are used to study its degradation upon repeated cycling. A comparison between the number of EPR-active sites and the number of electrochemically active charges, as measured by cyclic voltammetry, provides information on the nature of the degradation process. Low-temperature ex situ pulse EPR measurements on the oxidized polymer film reveal the spectrum of dilute nitroxide species, which may be associated with electrochemically inactive islands. These experiments pave the way for advanced EPR techniques for accurately determining distances between adjacent paramagnetic centers and thus for identifying performance-limiting loss mechanisms, which can eventually help develop strategies for making ORBs powerful contenders on the path towards sustainable electrochemical power sources

Thermal Expansion and Polymorphism of Slawsonite SrAl2Si2O8

Slawsonite’s (SrAl2Si2O8) structure evolutions depending on temperature (27–1000 °C) have been studied by in situ single-crystal X-ray diffraction. The SrO7 polyhedron expands regularly with the temperature increase. Silicon and aluminum cations are ordered in tetrahedral sites of the studied slawsonite; no significant changes in their distribution as temperature increases were observed. Slawsonite demonstrates a relatively high volume thermal expansion (αV = 23 × 10−6 °C−1) with high anisotropy, typical for framework feldspar-related minerals and synthetic compounds. It was found that, contrary to previously published data, the crystal structure of slawsonite is stable in the studied temperature range and no phase transitions occur up to 1000 °C. The role of Ca and Ba substitution for Sr and Al/Si ordering on polymorphism of natural MAl2Si2O8 (M = Ca, Sr, Ba) is herein discussed

Temperature-Induced Phase Transition in a Feldspar-Related Compound BaZn₂As₂O₈∙H₂O

The high-temperature (HT) behavior of BaAs2Zn2O8∙H2O was studied by in situ single-crystal X-ray diffraction (SCXRD) and hot stage Raman spectroscopy (HTRS) up to dehydration and the associated phase transition. During heating, the studied compound undergoes the dehydration process with the formation of BaAs2Zn2O8, which is stable up to at least 525 °C. The evolution of the fourteen main Raman bands was traced during heating. The abrupt shift of all Raman bands in the 70–1100 cm−1 spectral region was detected at 150 °C, whereas in the spectral region 3000–3600 cm−1 all the bands disappeared, which confirms the dehydration process of BaAs2Zn2O8∙H2O. The transition from BaAs2Zn2O8∙H2O to BaAs2Zn2O8 is accompanied by symmetry increasing from P21 to P21/c with the preservation of the framework topology. Depending on the research method, the temperature of the phase transition is 150 °C (HTRS) or 300 °C (HT SCXRD). According to the HT SCXRD data, in the temperature range 25–300 °C the studied compound demonstrates anisotropic thermal expansion (αmax/αmin = 9.4), which is explained by flexible crankshaft chains of TO4 (T = As, Zn) tetrahedra. Additionally, we discussed some crystal-chemical aspects of minerals with both (ZnOn) and (AsOm) polyhedra (n = 4, 5, 6; m = 3, 4) as main structural units

Glendonite-Like Carbonate Aggregates from the Lower Ordovician Koporye Formation (Russian Part of the Baltic Klint): Detailed Mineralogical and Geochemical Data and Paleogeographic Implications

Stellate and plate-like carbonate bodies, traditionally called anthraconites, are found throughout the Baltic-Ladoga Klint in bituminous shale of the Koporye Formation (Tremadocian, Lower Ordovician). Although this time interval is usually considered as a greenhouse, there is some evidence for the existence of at least temporary cold conditions during the Cambrian&ndash;Ordovician. However, the origin of anthraconites is still strongly debated. We studied the mineralogical, petrographic, cathodoluminescence, geochemical, and isotopic characteristics of anthraconites from five sections of the Russian part of the Baltic paleobasin. A close similarity between the morphological, petrographic, cathodoluminescence, and isotopic characteristics of the studied anthraconites with those of glendonites allow us to suggest that these bodies formed in a similar paleo-environment and should be considered as pseudomorphs of the mineral ikaite. The oxygen and carbon isotope ratios reveal that ikaite precipitation occurred in low-temperature conditions on the seafloor. The carbon isotopic values reveal influence of inorganic seawater carbon along with organic matter decomposition and/or methane oxidation during ikaite-glendonite transformations. The oxygen isotopic composition significantly changed after deposition due to meteoric diagenesis. We propose that the studied Tremadocian anthraconites formed under a region of upwelling, where cold phosphate-rich deep waters rose to the relatively shallow part of the Baltic paleobasin, providing favorable conditions for ikaite precipitation. Based on our cathodoluminescence study, we suggest that ikaite was transformed to calcite over several stages during diagenesis. Mineralogical studies also reveal that primary calcite was transformed to sulfate (gypsum) or dolomite during late superimposed processes

Key Features of TEMPO-Containing Polymers for Energy Storage and Catalytic Systems

The need for environmentally benign portable energy storage drives research on organic batteries and catalytic systems. These systems are a promising replacement for commonly used energy storage devices that rely on limited resources such as lithium and rare earth metals. The redox-active TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl-4-yl) fragment is a popular component of organic systems, as its benefits include remarkable electrochemical performance and decent physical properties. TEMPO is also known to be an efficient catalyst for alcohol oxidation, oxygen reduction, and various complex organic reactions. It can be attached to various aliphatic and conductive polymers to form high-loading catalysis systems. The performance and efficiency of TEMPO-containing materials strongly depend on the molecular structure, and thus rational design of such compounds is vital for successful implementation. We discuss synthetic approaches for producing electroactive polymers based on conductive and non-conductive backbones with organic radical substituents, fundamental aspects of electrochemistry of such materials, and their application in energy storage devices, such as batteries, redox-flow cells, and electrocatalytic systems. We compare the performance of the materials with different architectures, providing an overview of diverse charge interactions for hybrid materials, and presenting promising research opportunities for the future of this area

2-Hydroxy-3-octyloxybenzaldehyde

Herein, we report the chromatography-free synthesis of 2-hydroxy-3-octyloxybenzaldehyde by the alkylation of 2,3-dihydroxybenzaldehyde as a promising precursor for new SalEn-type complexes with transition metals. The structure of the product is elucidated by means of 1H and 13C-NMR spectra, high-resolution mass spectrometry with electrospray ionization (ESI-HRMS) and Fourier-transform infrared spectroscopy (FTIR)