Sensitive magnetometry reveals inhomogeneities in charge storage and weak transient internal currents in Li-ion cells.

The ever-increasing demand for high-capacity rechargeable batteries highlights the need for sensitive and accurate diagnostic technology for determining the state of a cell, for identifying and localizing defects, and for sensing capacity loss mechanisms. Here, we leverage atomic magnetometry to map the weak induced magnetic fields around Li-ion battery cells in a magnetically shielded environment. The ability to rapidly measure cells nondestructively allows testing even commercial cells in their actual operating conditions, as a function of state of charge. These measurements provide maps of the magnetic susceptibility of the cell, which follow trends characteristic for the battery materials under study upon discharge. In particular, hot spots of charge storage are identified. In addition, the measurements reveal the capability to measure transient internal current effects, at a level of µA, which are shown to be dependent upon the state of charge. These effects highlight noncontact battery characterization opportunities. The diagnostic power of this technique could be used for the assessment of cells in research, quality control, or during operation, and could help uncover details of charge storage and failure processes in cells.

Unusual Proton Transfer Kinetics in Water at the Temperature of Maximum Density.

Water exhibits numerous anomalous properties, many of which remain poorly understood. One of its intriguing behaviors is that it exhibits a temperature of maximum density (TMD) at 4 °C. We provide here new experimental evidence for hitherto unknown abrupt changes in proton transfer kinetics at the TMD. In particular, we show that the lifetime of OH^{-} ions has a maximum at this temperature, in contrast to hydronium ions. Furthermore, base-catalyzed proton transfer shows a sharp local minimum at this temperature, and activation energies change abruptly as well. The measured lifetimes agree with earlier theoretical predictions as the temperature approaches the TMD. Similar results are also found for heavy water at its own TMD. These findings point to a high propensity of forming fourfold coordinated OH^{-} solvation complexes at the TMD, underlining the asymmetry between hydroxide and hydronium transport. These results could help to further elucidate the unusual properties of water and related liquids.

Flow-Pattern Characterization of Biphasic Electrochemical Cells by Magnetic Resonance Imaging under Forced Hydrodynamic Conditions.

The fluid dynamics of a liquid|liquid system inside a four-electrode electrochemical cell were studied by velocimetry magnetic resonance imaging (MRI) and flow propagator measurements. To characterize this system fully, three different cell configurations operating at two rotational frequencies were analyzed. Quantitative information about the stability of the liquid|liquid interface and the dynamics of the organic phase were determined. The NMR spectroscopy results were in agreement with the electrochemical measurements performed by using the same experimental setup.

Spatially Resolved Monitoring of Drying of Hierarchical Porous Organic Networks.

Evaporation kinetics of water confined in hierarchal polymeric porous media is studied by low field nuclear magnetic resonance (NMR). Systems synthesized with various degrees of cross-linker density render networks with similar pore sizes but different response when soaked with water. Polymeric networks with low percentage of cross-linker can undergo swelling, which affects the porosity as well as the drying kinetics. The drying process is monitored macroscopically by single-sided NMR, with spatial resolution of 100 µm, while microscopic information is obtained by measurements of spin-spin relaxation times (T2). Transition from a funicular to a pendular regime, where hydraulic connectivity is lost and the capillary flow cannot compensate for the surface evaporation, can be observed from inspection of the water content in different sample layers. Relaxation measurements indicate that even when the larger pore structures are depleted of water, capillary flow occurs through smaller voids.

Enhanced Surface Interaction of Water Confined in Hierarchical Porous Polymers Induced by Hydrogen Bonding.

Hierarchical porous polymer systems are increasingly applied to catalysis, bioengineering, or separation technology because of the versatility provided by the connection of mesopores with percolating macroporous structures. Nuclear magnetic resonance (NMR) is a suitable technique for the study of such systems as it can detect signals stemming from the confined liquid and translate this information into pore size, molecular mobility, and liquid-surface interactions. We focus on the properties of water confined in macroporous polymers of ethylene glycol dimethacrylate and 2-hydroxyethyl methacrylate [poly(EGDMA-co-HEMA)] with different amounts of cross-linkers, in which a substantial variation of hydroxyl groups is achieved. As soft polymer scaffolds may swell upon saturation with determined liquids, the use of NMR is particularly important as it measures the system in its operational state. This study combines different NMR techniques to obtain information on surface interactions of water with hydrophilic polymer chains. A transition from a surface-induced relaxation in which relaxivity depends on the pore size to a regime where the organic pore surface strongly restricts water diffusion is observed. Surface affinities are defined through the molecular residence times near the network surface.

Evaporation kinetics in swollen porous polymeric networks.

NMR is a fast, nondestructive, and noninvasive technique that can provide information about the pore structure of macroporous polymer beads and the dynamics of liquids confined in them. In this work, we describe the study of the pore structure of the macroporous polymer of ethylene glycol dimethacrylate and 2-hydroxyethyl methacrylate [poly(EGDMA-co-HEMA)] in the dry but also in the swollen state by measuring relaxation times of liquids contained in the polymer network. The results show that the pore architecture differs from the dry to the soaked state. The behavior of polar liquids during evaporation and deswelling dynamics is monitored and described. An internal migration of water from the swollen polymer mesh into expanding pores takes place. With this procedure it is possible to obtain information about the microscopic morphology behavior of the matrix during evaporation and deswelling. This information is of great interest with the aspect of possible and future applications for these types of materials.

Quadrupolar 23Na+ NMR relaxation as a probe of subpicosecond collective dynamics in aqueous electrolyte solutions.

Nuclear magnetic resonance relaxometry represents a powerful tool for extracting dynamic information. Yet, obtaining links to molecular motion is challenging for many ions that relax through the quadrupolar mechanism, which is mediated by electric field gradient fluctuations and lacks a detailed microscopic description. For sodium ions in aqueous electrolytes, we combine ab initio calculations to account for electron cloud effects with classical molecular dynamics to sample long-time fluctuations, and obtain relaxation rates in good agreement with experiments over broad concentration and temperature ranges. We demonstrate that quadrupolar nuclear relaxation is sensitive to subpicosecond dynamics not captured by previous models based on water reorientation or cluster rotation. While ions affect the overall water retardation, experimental trends are mainly explained by dynamics in the first two solvation shells of sodium, which contain mostly water. This work thus paves the way to the quantitative understanding of quadrupolar relaxation in electrolyte and bioelectrolyte systems.

Comparison of experimental times in T1-D and D-T2 correlation experiments in single-sided NMR.

Diffusion-relaxation correlation experiments in nuclear magnetic resonance are a powerful technique for the characterization of fluid dynamics in confined geometries or soft matter, in which relaxation may be either spin-spin (T2) or spin-lattice (T1). The general approach is to acquire a set of bidimensional data in which diffusion is codified by the evolution of the magnetization with either Hahn or stimulated echoes (STE) in the presence of a constant magnetic field gradient. While T2 is codified by a Carr-Purcell-Meiboom-Gil (CPMG) sequence, T1 is either encoded by saturation or inversion-recovery methods. In this work, we analyse the measurement time of diffusion-relaxation times in single-sided NMR and show that T1-D acquisition is always shorter than D-T2. Depending on the hardware characteristics, this time reduction can be up to an order of magnitude. We present analytical calculations and examples in model porous media saturated with water and in a dairy product.

Diagnosing current distributions in batteries with magnetic resonance imaging.

Batteries and their defects are notoriously difficult to analyze non-destructively, and consequently, many defects and failures remain little noticed and characterized until they cause grave damage. The measurement of the current density distributions inside a battery could reveal information about deviations from ideal cell behavior, and could thus provide early signs of deterioration or failures. Here, we describe methodology for fast nondestructive assessment and visualization of the effects of current distributions inside Li-ion pouch cells. The technique, based on magnetic resonance imaging (MRI), allows measuring magnetic field maps during charging/discharging. Marked changes in the distributions are observed as a function of the state of charge, and also upon sustaining damage. In particular, it is shown that nonlinearities and asymmetries of current distributions could be mapped at different charge states. Furthermore, hotspots of current flow are also shown to correlate with hotspots in charge storage. This technique could potentially be of great utility in diagnosing the health of cells and their behavior under different charging or environmental conditions.

Multinuclear absolute magnetic resonance thermometry.

Non-invasive measurement of absolute temperature is important for proper characterization of various pathologies and for evaluation of thermal dose during interventional procedures. The proton (hydrogen nucleus) magnetic resonance (MR) frequency shift method can be used to map relative temperature changes. However, spatiotemporal variations in the main magnetic field and the lack of local internal frequency reference challenge the determination of absolute temperature. Here, we introduce a multinuclear method for absolute MR thermometry, based on the fact that the hydrogen and sodium nuclei exhibit a unique and distinct characteristic frequency dependence with temperature and with electrolyte concentration. A one-to-one mapping between the precession frequency difference of the two nuclei and absolute temperature is demonstrated. Proof-of-concept experiments were conducted in aqueous solutions with different NaCl concentrations, in agarose gel samples, and in freshly excised ex vivo mouse tissues. One-dimensional chemical shift imaging experiments also demonstrated excellent agreement with infrared measurements.

Single-shot velocity mapping by rewinding of velocity encoding with Echo-Planar Imaging.

The ability of single-shot NMR imaging methods to follow the time evolution of a velocity distribution within an object is strongly limited by the phase errors accumulated as velocity maps are acquired. In the particular case of Carr-Purcell based sequences combined with Echo Planar Imaging acquisition, phase accumulates through subsequent images, hampering the possibility to acquire several velocity maps, which would be useful to determine transient behavior. In this work, we propose the use of a rewinding velocity encoding module applied after the acquisition of each image during the CPMG echo train. In this way, the first velocity module imparts a velocity dependent phase prior to the image acquisition and the second pair cancels this phase out before the next refocusing radiofrequency pulse is applied. The performance and limits of this method are studied by acquiring 100 images of a co-rotating Couette cell over a period of 1.6 s as a function of the rotation speed. The method is applied to determine the kinematic viscosity of a water/alcohol mixture, which is a relevant topic in many physical, chemical and biological processes.

Probing numerical Laplace inversion methods for two and three-site molecular exchange between interconnected pore structures.

Two-dimension (2D) Nuclear Magnetic Resonance relaxometry experiments are a powerful tool extensively used to probe the interaction among different pore structures, mostly in inorganic systems. The analysis of the collected experimental data generally consists of a 2D numerical inversion of time-domain data where T2-T2 maps are generated. Through the years, different algorithms for the numerical inversion have been proposed. In this paper, two different algorithms for numerical inversion are tested and compared under different conditions of exchange dynamics; the method based on Butler-Reeds-Dawson (BRD) algorithm and the fast-iterative shrinkage-thresholding algorithm (FISTA) method. By constructing a theoretical model, the algorithms were tested for a two- and three-site porous media, varying the exchange rates parameters, the pore sizes and the signal to noise ratio. In order to test the methods under realistic experimental conditions, a challenging organic system was chosen. The molecular exchange rates of water confined in hierarchical porous polymeric networks were obtained, for a two- and three-site porous media. Data processed with the BRD method was found to be accurate only under certain conditions of the exchange parameters, while data processed with the FISTA method is precise for all the studied parameters, except when SNR conditions are extreme.

Monitoring Molecular Transport across Colloidal Membranes.

The controlled shaping and surface functionalization of colloidal particles has provided opportunities for the development of new materials and responsive particles. The possibility of creating hollow particles with semipermeable walls allows modulating molecular transport properties on colloidal length scales. While shapes and sizes can typically be observed by optical means, the underlying chemical and physical properties are often invisible. Here, we present measurements of cross-membrane transport via pulsed field gradient NMR in packings of hollow colloidal particles. The work is conducted using a systematic selection of particle sizes, wall permeabilities, and osmotic pressures and allows tracking organic molecules as well as ions. It is also shown that, while direct transport of molecules can be measured, indirect markers can be obtained for invisible species via the osmotic pressure as well. The cross-membrane transport information is important for applications in nanoconfinement, nanofiltration, nanodelivery, or nanoreactor devices.

Desktop MRI as a promising tool for mapping intra-aneurismal flow.

In this work we evaluate the performance of a 40-mm diameter bore 0.2T desktop Halbach tomograph to obtain 2D and 3D velocity maps for studying intra-aneurismal flow in the presence or absence of nitinol meshed implants with the aim of optimizing the flow diverter efficacy. Phantoms with known spatial velocity distribution were used to determine the performance of the MRI system. Maximum velocities of about 200mm/s could be measured with a precision of 1% at a spatial resolution of 0.5×0.5×1mm(3). This accuracy is suitable to evaluate in vitro intra-aneurismal flow under different conditions such as variable flow rates, different vessel-aneurysm geometry, as well as the influence of metallic flow diverters on the intra-aneurismal flow distribution. The information obtained non-invasively with desktop tomographs can be used to complement in vivo studies in order to decide the optimum flow diverter.