Laplace inverted pulsed EPR relaxation to study contact between active material and carbon black in Li-organic battery cathodes.

The addition of conductive additives during electrode fabrication is standard practice to mitigate a low intrinsic electronic conductivity of most cathode materials used in Li-ion batteries. To ensure an optimal conduction pathway, these conductive additives, which generally consist of carbon particles, need to be in good contact with the active compounds. Herein, we demonstrate how a combination of pulsed electron paramagnetic resonance (EPR) relaxometry and inverse Laplace transform (ILT) can be used to study such contact. The investigated system consists of PTMA (poly(2,2,6,6-tetramethylpiperidinyloxy-4-ylmethacrylate)) monomer radicals, which is a commonly used redox unit in organic radical batteries (ORB), mixed at different ratios with Super P carbon black (CB) as the conductive additive. Inversion recovery data were acquired to determine longitudinal (T1) relaxation time constant distributions. It was observed that not only the position and relative amplitude, but also the number of relaxation modes varies as the composition of PTMA monomer and CB is changed, thereby justifying the use of ILT instead of fitting with a predetermined number of components. A hypothesis for the origin of different relaxation modes was devised. It suggests that the electrode composition may locally affect the quality of electronic contact between the active material and carbon black.

Dynamics of [Pyr13][Tf2N] ionic liquid confined to carbon black.

The intrinsic ionic nature of room temperature ionic liquids (RTILs) bears the potential to replace classical aqueous electrolytes in electrochemical applications, for example in metal-air batteries. For a systematic adjustment of RTIL properties in porous cathodes, the ionic arrangement under confinement is of prime importance. Using spectrally resolved pulsed gradient stimulated echo nuclear magnetic resonance (PGSTE-NMR) and spin-lattice NMR relaxation time (T1) distributions, the dynamics of 1-methyl-1-propylpyrrolidiniumbis(trifluoromethylsulfonyl)imide ([Pyr13][Tf2N]) confined to carbon black were investigated. A considerable dependence of the [PYR13] mobility on the loading fraction of the carbon black pore space was found. There is evidence for a preferential layering of the RTIL adjacent to the carbon surface and a dependence of the ionic configuration on the local structure of the carbon surface. The inversion efficiency of inversion-recovery T1 data indicates a quasi-stationary layer at the carbon surface with solid-like properties, where the bulk-like properties of the RTIL are adopted as the distance to the surface increases. From the NMR diffusion data an intermediate layer between the quasi-stationary and the bulk-like RTIL is evident. This layer shows a particularly strong pore space loading dependence. While it has an anisotropic, two-dimensional mobility with reduced diffusion perpendicular to the surface at any loading, when it interfaces a gas phase at low loading its mobility is higher than bulk diffusion by up to an order of magnitude and chemical exchange with other layers is low. This layer appears to be of particular importance for the ion exchange between RTIL environments with different spacing from the carbon surface and hence crucial for the overall dynamics of RTILs in the investigated porous environment.

Long-run in operando NMR to investigate the evolution and degradation of battery cells.

To improve the lifetime of lithium-ion batteries, a detailed understanding of the degradation mechanisms is essential. Nuclear magnetic resonance (NMR) is able to unravel the reversible as well as irreversible transient changes of composition, shape and morphology in a battery cell. Using a newly developed cylindrical battery container free of metallic components in combination with a numerically optimized saddle coil, in operando NMR investigations of battery cells over hundreds of charge/discharge cycles are presented. Alternating with NMR data acquisition, electrochemical impedance spectra (EIS) can be recorded, which enables correlative analysis of the two techniques. Long-run in operando NMR measurements on a Li metal vs. graphite cell reveal the formation and evolution of mossy and dendritic Li microstructures over a period of 1000 h, which illustrates the capabilities of NMR to identify dendrite mitigation strategies in cells operated under realistic conditions.

Monitoring local redox processes in LiNi0.5Mn1.5O4 battery cathode material by in operando EPR spectroscopy.

Despite the multitude of analytical methods available to characterize battery cathode materials, identifying the factors responsible for material aging is still challenging. We present the first investigation of transient redox processes in a spinel cathode during electrochemical cycling of a lithium ion battery by in operando electron paramagnetic resonance (EPR). The battery contains a LiNi0.5Mn1.5O4 (LNMO) spinel cathode, which is a material whose magnetic interactions are well understood. The evolution of the EPR signal in combination with electrochemical measurements shows the impact of Mn3+ on the Li+ motion inside the spinel. Moreover, state of charge dependent linewidth variations confirm the formation of a solid solution for slow cycling, which is taken over by mixed models of solid solution and two-phase formation for fast cycling due to kinetic restrictions and overpotentials. Long-term measurements for 480 h showed the stability of the investigated LNMO, but also small amounts of cathode degradation products became visible. The results point out how local, exchange mediated magnetic interactions in cathode materials are linked with battery performance and can be used for material characterization.

Singlet Oxygen Formation during the Charging Process of an Aprotic Lithium-Oxygen Battery.

Aprotic lithium-oxygen (Li-O2 ) batteries have attracted considerable attention in recent years owing to their outstanding theoretical energy density. A major challenge is their poor reversibility caused by degradation reactions, which mainly occur during battery charge and are still poorly understood. Herein, we show that singlet oxygen ((1) Δg ) is formed upon Li2 O2 oxidation at potentials above 3.5 V. Singlet oxygen was detected through a reaction with a spin trap to form a stable radical that was observed by time- and voltage-resolved in operando EPR spectroscopy in a purpose-built spectroelectrochemical cell. According to our estimate, a lower limit of approximately 0.5 % of the evolved oxygen is singlet oxygen. The occurrence of highly reactive singlet oxygen might be the long-overlooked missing link in the understanding of the electrolyte degradation and carbon corrosion reactions that occur during the charging of Li-O2 cells.

In operando NMR investigations of the aqueous electrolyte chemistry during electrolytic CO2 reduction.

The electrolytic reduction of CO2 in aqueous media promises a pathway for the utilization of the green house gas by converting it to base chemicals or building blocks thereof. However, the technology is currently not economically feasible, where one reason lies in insufficient reaction rates and selectivities. Current research of CO2 electrolysis is becoming aware of the importance of the local environment and reactions at the electrodes and their proximity, which can be only assessed under true catalytic conditions, i.e. by in operando techniques. In this work, multinuclear in operando NMR techniques were applied in order to investigate the evolution of the electrolyte chemistry during CO2 electrolysis. The CO2 electroreduction was performed in aqueous NaHCO3 or KHCO3 electrolytes at silver electrodes. Based on 13C and 23Na NMR studies at different magnetic fields, it was found that the dynamic equilibrium of the electrolyte salt in solution, existing as ion pairs and free ions, decelerates with increasingly negative potential. In turn, this equilibrium affects the resupply rate of CO2 to the electrolysis reaction from the electrolyte. Substantiated by relaxation measurements, a mechanism was proposed where stable ion pairs in solution catalyze the bicarbonate dehydration reaction, which may provide a new pathway for improving educt resupply during CO2 electrolysis.

Electrolyte contact changes nano-Li4Ti5O12 bulk properties via surface polarons.

It is of general interest to combine the faradaic processes based high energy density of a battery with the non-faradaic processes based high power density of a capacitor in one cell. Surface area and functional groups of electrode materials strongly affect these properties. For the anode material Li4Ti5O12 (LTO), we suggest a polaron based mechanism that influences Li ion uptake and mobility. Here we show electrolytes containing a lithium salt induce an observable change in the bulk NMR relaxation properties of LTO nano particles. The longitudinal 7Li NMR relaxation time of bulk LTO can change by almost an order of magnitude and, therefore, reacts very sensitively to the cation and its concentration in the surrounding electrolyte. The reversible effect is largely independent of the used anions and of potential anion decomposition products. It is concluded that lithium salt containing electrolytes increase the mobility of surface polarons. These polarons and additional lithium cations from the electrolyte can now diffuse through the bulk, induce the observed enhanced relaxation rate and enable the non-faradaic process. This picture of a Li+ ion equilibrium between electrolyte and solid may help with improving the charging properties of electrode materials.

Interplay between defect structure and catalytic activity in the Mo(10-x)V(x)O(y) mixed-oxide system.

The Mo(10-x)V(x)O(y) solid-solution systems (0≤x≤10) were studied by electron paramagnetic resonance spectroscopy. The results show the existence of paramagnetic vanadyl VO(2+) species, whose concentration becomes maximal for Mo(5)V(5)O(y·). A quantitative analysis of the [VO(2+)] concentration as a function of the Mo/V ratio allows it to characterize the prevailing defect chemistry in the Mo(10-x)V(x)O(y) system. In this respect, the semi-conducting properties of Mo(10-x)V(x)O(y) are p-type in an interval of Mo(9)V(1)O(y)-Mo(5)V(5)O(y) and switch into n-type because of the conduction electrons in a composition range of Mo(5)V(5)O(y)-Mo(1)V(9)O(y). Highest catalytic activity is obtained when vanadium acts as an acceptor center and oxygen vacancies ν(··)(O) are formed for reasons of charge compensation. In addition to the surface, ν(··)(O) and VO(2+) centers in the bulk have to be considered too for heterogeneous catalysis.

Local coordination of Fe3+ in Li[Co(0.98)Fe(0.02)]O2 as cathode material for lithium ion batteries-multi-frequency EPR and Monte-Carlo Newman-superposition model analysis.

The local coordination of the Fe(3+)-centers in Li[Co(0.98)Fe(0.02)]O(2) cathode materials for lithium-ion batteries has been investigated by means of XRD and multi-frequency EPR spectroscopy. EPR clearly showed the Fe(3+) being in a high-spin state with S = 5/2. The set of spin-Hamiltonian parameters obtained from multi-frequency EPR experiments with Larmor frequencies ranging between 9.8 and 406 GHz was transformed into structural information by means of an expansion to standard Newton-superposition modeling, termed as Monte-Carlo Newman superposition modeling. Based on this analysis, an isovalent incorporation of the Fe(3+)-ions on the Co(3+)-sites, i.e. Fe(x)(Co), has been shown. With that respect, the positive sign of the axial second-order fine-structure interaction parameter B(0)(2) is indicative of an elongated oxygen octahedron, whereas B(0)(2) < 0 points to a compressed octahedron coordinated about the Fe(3+)-center. Furthermore, the results obtained here suggest that the oxygen octahedron about the Fe(3+)-ion is slightly distorted as compared to the CoO(6) octahedron, which in turn may impose mechanical strain to the cathode material.

An electrochemical cell for in operando 13C nuclear magnetic resonance investigations of carbon dioxide/carbonate processes in aqueous solution.

In operando nuclear magnetic resonance (NMR) spectroscopy is one method for the online investigation of electrochemical systems and reactions. It allows for real-time observations of the formation of products and intermediates, and it grants insights into the interactions of substrates and catalysts. An in operando NMR setup for the investigation of the electrolytic reduction of CO2 at silver electrodes has been developed. The electrolysis cell consists of a three-electrode setup using a working electrode of pristine silver, a chlorinated silver wire as the reference electrode, and a graphite counter electrode. The setup can be adjusted for the use of different electrode materials and fits inside a 5 mm NMR tube. Additionally, a shielding setup was employed to minimize noise caused by interference of external radio frequency (RF) waves with the conductive components of the setup. The electrochemical performance of the in operando electrolysis setup is compared with a standard CO2 electrolysis cell. The small cell geometry impedes the release of gaseous products, and thus it is primarily suited for current densities below 1 mA cm-2. The effect of conductive components on 13C NMR experiments was studied using a CO2-saturated solution of aqueous bicarbonate electrolyte. Despite the B0 field distortions caused by the electrodes, a proper shimming could be attained, and line widths of ca. 1 Hz were achieved. This enables investigations in the sub-Hertz range by NMR spectroscopy. High-resolution 13C NMR and relaxation time measurements proved to be sensitive to changes in the sample. It was found that the dynamics of the bicarbonate electrolyte varies not only due to interactions with the silver electrode, which leads to the formation of an electrical double layer and catalyzes the exchange reaction between CO2 and HCO3-, but also due to interactions with the electrochemical setup. This highlights the necessity of a step-by-step experiment design for a mechanistic understanding of processes occurring during electrochemical CO2 reduction.

EPR Imaging of Metallic Lithium and its Application to Dendrite Localisation in Battery Separators.

Conduction Electron Paramagnetic Resonance Imaging (CEPRI) is presented as a sensitive technique for mapping metallic lithium species. The method is demonstrated using different samples that are either thick or thin compared to the microwave skin depth. As a thin sample, microstructured metallic lithium deposits in a lithium-ion battery (LIB) separator were analysed, illustrating the capabilities of CEPRI by obtaining a high-resolution image with an image resolution in the micrometre range. Limitations and intricacies of the method due to non-linear effects caused by the skin effect are discussed based on images of surface patterns on thick metallic lithium samples. The lineshape of the EPR spectrum is introduced as a proxy to determine the suitability of CEPRI for the quantitative visualisation of metallic lithium deposits. The results suggest that CEPRI is particularly suited to analyse the spatial distribution of microstructured Li that forms during charging and discharging of LIB cells, including the localization of the point of failure in the case of an internal cell short circuit caused by dendrites.

3D printed sample holder for in-operando EPR spectroscopy on high temperature polymer electrolyte fuel cells.

Electrochemical cells contain electrically conductive components, which causes various problems if such a cell is analyzed during operation in an EPR resonator. The optimum cell design strongly depends on the application and it is necessary to make certain compromises that need to be individually arranged. Rapid prototyping presents a straightforward option to implement a variable cell design that can be easily adapted to changing requirements. In this communication, it is demonstrated that sample containers produced by 3D printing are suitable for EPR applications, with a particular emphasis on electrochemical applications. The housing of a high temperature polymer electrolyte fuel cell (HT-PEFC) with a phosphoric acid doped polybenzimidazole membrane was prepared from polycarbonate by 3D printing. Using a custom glass Dewar, this fuel cell could be operated at temperatures up to 140°C in a standard EPR cavity. The carbon-based gas diffusion layer showed an EPR signal with a characteristic Dysonian line shape, whose evolution could be monitored in-operando in a non-invasive manner.

Unraveling the Degradation Process of LiNi0.8Co0.15Al0.05O2 Electrodes in Commercial Lithium Ion Batteries by Electronic Structure Investigations.

The degradation of LiNi0.8Co0.15Al0.05O2 (LNCAO) is reflected by the electrochemical performance in the fatigued state and correlated with the redox behavior of these cathodes. The detailed electrochemical performance of these samples is investigated by galvanostatic and voltammetric cycling as well as with the galvanostatic intermittent titration technique (GITT). Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy was used to investigate the oxidation state of all three materials at the Ni L2,3, O K, and Co L2,3 edges at five different states of charge. Surface and more bulklike properties are distinguished by total electron yield (TEY) and fluorescence yield (FY) measurements. The electrochemical investigations revealed that the changes in the cell performance of the differently aged materials can be explained by considering the reaction kinetics of the intercalation/deintercalation process. The failure of the redox process of oxygen and nickel at low voltages leads to a significant decrease of the reaction rates in the fatigued cathodes. The accompanied cyclic voltammogram (CV) peaks appear as two peaks because of the local minimum of the reaction rate, although it is one peak in the CV of the calendarically aged LNCAO. The absence of the oxidation/reduction process at low voltages can be traced back to changes in the surface morphology (formation of a NiO-like structure). Further consequences of these material changes are overpotentials, which lead to capacity losses of up to 30% (cycled with a C/3 rate).

Analyzing the defect structure of CuO-doped PZT and KNN piezoelectrics from electron paramagnetic resonance.

The defect structure for copper-doped sodium potassium niobate (KNN) ferroelectrics has been analyzed with respect to its defect structure. In particular, the interplay between the mutually compensating dimeric (Cu(Nb)'''-V(O)··) and trimeric (V(O)··-Cu(Nb)'''-V(O)··)· defect complexes with 180° and non-180° domain walls has been analyzed and compared to the effects from (Cu'' - V(O)··)(x)× dipoles in CuO-doped lead zirconate titanate (PZT). Attempts are made to relate the rearrangement of defect complexes to macroscopic electromechanical properties.

Limitation of discharge capacity and mechanisms of air-electrode deactivation in silicon-air batteries.

The electrocatalytical process at the air cathode in novel silicon-air batteries using the room-temperature ionic liquid hydrophilic 1-ethyl-3-methylimidazolium oligofluorohydrogenate [EMI⋅2.3 HF⋅F] as electrolyte and highly doped silicon wafers as anodes is investigated by electrochemical means, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR) spectroscopy. The results obtained by XPS and EPR provide a model to describe the limited discharge capacity by means of a mechanism of air-electrode deactivation. In that respect, upon discharge the silicon-air battery's cathode is not only blocked by silicon oxide reduction products, but also experiences a major modification in the MnO2 catalyst nature. The proposed modification of the MnO2 catalyst by means of a MnF2 surface layer greatly impacts the Si-air performance and describes a mechanism relevant for other metal-air batteries, such as the lithium-air. Moreover, the ability for this deactivation layer to form is greatly impacted by water in the electrolyte.

Defect structure in aliovalently-doped and isovalently-substituted PbTiO3 nano-powders.

The defect structure of Fe(3+)-, Cu(2+)-, Mn(4+)- and Gd(3+)-doped PbTiO(3) nano-powders has been studied by electron paramagnetic resonance (EPR) spectroscopy. Analogous to the situation for 'bulk' ferroelectrics, Fe(3+) and Cu(2+) act as acceptor-type functional centers that form defect complexes with charge-compensating oxygen vacancies. The corresponding defect dipoles are aligned along the direction of spontaneous polarization, P(S), and possess an additional defect polarization, P(D). Upon the transition to the nano-regime, the defect structure is modified such that orientations perpendicular to P(S), [Formula: see text] and [Formula: see text] also become realized. Moreover, the binding energy for the defect complexes is lowered such that instead 'free' Fe'(Ti) and V··(O)-centers are formed. As a consequence, the concentration of mobile V··(O) that enhances the ionic conductivity through drift diffusion is increased for the nano-powders. Finally, in the nano-regime the ferroelectric 'hardening' is expected to be considerably decreased as compared to the 'bulk' compounds. In contrast to the acceptor-type dopants, the donor-type Gd(3+) dopant is incorporated as an 'isolated' functional center, where charge compensation by means of lead vacancies is performed in distant coordination spheres.