There is an ever-increasing need for advanced batteries for portable electronics, to power electric vehicles and to facilitate the distribution and storage of energy derived from renewable energy sources. The increasing demands on batteries and other electrochemical devices have spurred research into the development of new electrode materials that could lead to better performance and lower cost (increased capacity, stability and cycle life, and safety). These developments have, in turn, given rise to a vigorous search for the development of robust and reliable diagnostic tools to monitor and analyse battery performance, where possible, in situ. Yet, a proven, convenient and non-invasive technology, with an ability to image in three dimensions the chemical changes that occur inside a full battery as it cycles, has yet to emerge. Here we demonstrate techniques based on magnetic resonance imaging, which enable a completely non-invasive visualization and characterization of the changes that occur on battery electrodes and in the electrolyte. The current application focuses on lithium-metal batteries and the observation of electrode microstructure build-up as a result of charging. The methods developed here will be highly valuable in the quest for enhanced battery performance and in the evaluation of other electrochemical devices.

Lithium dendrite growth in lithium ion and lithium rechargeable batteries is associated with severe safety concerns. To overcome these problems, a fundamental understanding of the growth mechanism of dendrites under working conditions is needed. In this work, in situ (7)Li magnetic resonance (MRI) is performed on both the electrolyte and lithium metal electrodes in symmetric lithium cells, allowing the behavior of the electrolyte concentration gradient to be studied and correlated with the type and rate of microstructure growth on the Li metal electrode. For this purpose, chemical shift (CS) imaging of the metal electrodes is a particularly sensitive diagnostic method, enabling a clear distinction to be made between different types of microstructural growth occurring at the electrode surface and the eventual dendrite growth between the electrodes. The CS imaging shows that mossy types of microstructure grow close to the surface of the anode from the beginning of charge in every cell studied, while dendritic growth is triggered much later. Simple metrics have been developed to interpret the MRI data sets and to compare results from a series of cells charged at different current densities. The results show that at high charge rates, there is a strong correlation between the onset time of dendrite growth and the local depletion of the electrolyte at the surface of the electrode observed both experimentally and predicted theoretical (via the Sand's time model). A separate mechanism of dendrite growth is observed at low currents, which is not governed by salt depletion in the bulk liquid electrolyte. The MRI approach presented here allows the rate and nature of a process that occurs in the solid electrode to be correlated with the concentrations of components in the electrolyte.

The growth of lithium microstructures during battery cycling has, to date, prohibited the use of Li metal anodes and raises serious safety concerns even in conventional lithium-ion rechargeable batteries, particularly if they are charged at high rates. The electrochemical conditions under which these Li microstructures grow have, therefore, been investigated by in situ nuclear magnetic resonance (NMR), scanning electron microscopy (SEM) and susceptibility calculations. Lithium metal symmetric bag cells containing LiPF 6 in EC: DMC electrolytes were used. Distinct 7 Li NMR resonances were observed due to the Li metal bulk electrodes and microstructures, the changes in peak positions and intensities being monitored in situ during Li deposition. The changes in the NMR spectra, observed as a function of separator thickness and porosity (using Celgard and Whatmann glass microfiber membranes) and different applied pressures, were correlated with changes in the type of microstructure, by using SEM. Isotopically enriched 6 Li metal electrodes were used against natural abundance predominantly 7 Li metal counter electrodes to investigate radiofrequency (rf) field penetration into the Li anode and to confirm the assignment of the higher frequency peak to Li dendrites. The conclusions were supported by calculations performed to explore the effect of the different microstructures on peak position/broadening, the study showing that Li NMR spectroscopy can be used as a sensitive probe of the both the amount and type of microstructure formation.

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Lithium metal is a promising anode material for Li-ion batteries due to its high theoretical specific capacity and low potential. The growth of dendrites is a major barrier to the development of high capacity, rechargeable Li batteries with lithium metal anodes, and hence, significant efforts have been undertaken to develop new electrolytes and separator materials that can prevent this process or promote smooth deposits at the anode. Central to these goals, and to the task of understanding the conditions that initiate and propagate dendrite growth, is the development of analytical and nondestructive techniques that can be applied in situ to functioning batteries. MRI has recently been demonstrated to provide noninvasive imaging methodology that can detect and localize microstructure buildup. However, until now, monitoring dendrite growth by MRI has been limited to observing the relatively insensitive metal nucleus directly, thus restricting the temporal and spatial resolution and requiring special hardware and acquisition modes. Here, we present an alternative approach to detect a broad class of metallic dendrite growth via the dendrites' indirect effects on the surrounding electrolyte, allowing for the application of fast 3D 1 H MRI experiments with high resolution. We use these experiments to reconstruct 3D images of growing Li dendrites from MRI, revealing details about the growth rate and fractal behavior. Radiofrequency and static magnetic field calculations are used alongside the images to quantify the amount of the growing structures.Li-ion batteries | in situ MRI | dendrite growth L ithium metal is a promising anode material for secondary lithium batteries because it has the highest theoretical specific capacity of possible anode materials (3,860 mAh/g), and the most negative voltage. The metal's use is currently limited due to irregular microstructure buildup on the electrode during charging (1). These mossy, needle-like, or dendritic structures severely compromise battery performance and can eventually penetrate the separator and cause overheating and short circuiting, thus presenting serious safety concerns. Preventing dendrite growth has proven to be extremely challenging, due in part to the current poor understanding of the conditions under which the dendrites' growth is initiated and the factors that contribute to their continued growth (2, 3). The development of new analytical techniques that are sensitive to dendrite growth and amenable to studying electrochemical cells in situ is crucial to future efforts of improving battery designs and performance (4, 5).In situ NMR spectroscopy and MRI are powerful noninvasive methods that can provide time-resolved and quantitative information about the changes within the electrolyte and the electrodes. NMR measurements are sensitive to dendrite growth and are also able to resolve different lithium microstructure morphologies through chemical shift measurements (6-9). MRI approaches provide additional spatial information, allowing specific structural changes ...