In situ NMR and electrochemical quartz crystal microbalance techniques reveal the structure of the electrical double layer in supercapacitors.

Supercapacitors store charge through the electrosorption of ions on microporous electrodes. Despite major efforts to understand this phenomenon, a molecular-level picture of the electrical double layer in working devices is still lacking as few techniques can selectively observe the ionic species at the electrode/electrolyte interface. Here, we use in situ NMR to directly quantify the populations of anionic and cationic species within a working microporous carbon supercapacitor electrode. Our results show that charge storage mechanisms are different for positively and negatively polarized electrodes for the electrolyte tetraethylphosphonium tetrafluoroborate in acetonitrile; for positive polarization charging proceeds by exchange of the cations for anions, whereas for negative polarization, cation adsorption dominates. In situ electrochemical quartz crystal microbalance measurements support the NMR results and indicate that adsorbed ions are only partially solvated. These results provide new molecular-level insight, with the methodology offering exciting possibilities for the study of pore/ion size, desolvation and other effects on charge storage in supercapacitors

New Perspectives on the Charging Mechanisms of Supercapacitors.

Supercapacitors (or electric double-layer capacitors) are high-power energy storage devices that store charge at the interface between porous carbon electrodes and an electrolyte solution. These devices are already employed in heavy electric vehicles and electronic devices, and can complement batteries in a more sustainable future. Their widespread application could be facilitated by the development of devices that can store more energy, without compromising their fast charging and discharging times. In situ characterization methods and computational modeling techniques have recently been developed to study the molecular mechanisms of charge storage, with the hope that better devices can be rationally designed. In this Perspective, we bring together recent findings from a range of experimental and computational studies to give a detailed picture of the charging mechanisms of supercapacitors. Nuclear magnetic resonance experiments and molecular dynamics simulations have revealed that the electrode pores contain a considerable number of ions in the absence of an applied charging potential. Experiments and computer simulations have shown that different charging mechanisms can then operate when a potential is applied, going beyond the traditional view of charging by counter-ion adsorption. It is shown that charging almost always involves ion exchange (swapping of co-ions for counter-ions), and rarely occurs by counter-ion adsorption alone. We introduce a charging mechanism parameter that quantifies the mechanism and allows comparisons between different systems. The mechanism is found to depend strongly on the polarization of the electrode, and the choice of the electrolyte and electrode materials. In light of these advances we identify new directions for supercapacitor research. Further experimental and computational work is needed to explain the factors that control supercapacitor charging mechanisms, and to establish the links between mechanisms and performance. Increased understanding and control of charging mechanisms should lead to new strategies for developing next-generation supercapacitors with improved performances.The authors acknowledge the Sims Scholarship Cambridge (A.C.F.), the School of the Physical Sciences of the University of Cambridge (via an Oppenheimer Research Fellowship, C.M.), EPSRC (via the Supergen consortium, A.C.F. and J.M.G.), and the EU ERC (via an Advanced Fellowship to C.P.G.) for funding. We thank Nicole Trease, Andrew Ilott, Phoebe Allan, Elizabeth Humphreys, Paul Bayley, Hao Wang, Patrice Simon, Wan-Yu Tsai, Yury Gogotsi, Mathieu Salanne, Benjamin Rotenberg, Alexei Kornyshev, Svyatoslav Kondrat and Volker Presser for collaboration, and stimulating discussions and insights into supercapacitors over the course of our research on this subject.This is the final version of the article. It first appeared from the American Chemical Society via https://doi.org/10.1021/jacs.6b0211

Lattice simulation method to model diffusion and NMR spectra in porous materials.

A coarse-grained simulation method to predict nuclear magnetic resonance (NMR) spectra of ions diffusing in porous carbons is proposed. The coarse-grained model uses input from molecular dynamics simulations such as the free-energy profile for ionic adsorption, and density-functional theory calculations are used to predict the NMR chemical shift of the diffusing ions. The approach is used to compute NMR spectra of ions in slit pores with pore widths ranging from 2 to 10 nm. As diffusion inside pores is fast, the NMR spectrum of an ion trapped in a single mesopore will be a sharp peak with a pore size dependent chemical shift. To account for the experimentally observed NMR line shapes, our simulations must model the relatively slow exchange between different pores. We show that the computed NMR line shapes depend on both the pore size distribution and the spatial arrangement of the pores. The technique presented in this work provides a tool to extract information about the spatial distribution of pore sizes from NMR spectra. Such information is difficult to obtain from other characterisation techniques.C.M. acknowledges the School of the Physical Sciences of the University of Cambridge for funding through an Oppenheimer Research Fellowship. C.M., A.C.F., J.M.G., and C.P.G. acknowledge the Sims Scholarship (A.C.F.), EPSRC (via the Supergen consortium, J.M.G.), and the EU ERC (via an Advanced Fellowship to C.P.G.) for funding. A.C.F. and J.M.G. thank the NanoDTC Cambridge for travel funding. D.F. acknowledges EPSRC Grant No. EP/I000844/1.This is the final published version. It first appeared at http://scitation.aip.org/content/aip/journal/jcp/142/9/10.1063/1.4913368

New Insights into the Structure of Nanoporous Carbons from NMR, Raman, and Pair Distribution Function Analysis

The structural characterization of nanoporous carbons is a challenging task as they generally lack long-range order and can exhibit diverse local structures. Such characterization represents an important step toward understanding and improving the properties and functionality of porous carbons, yet few experimental techniques have been developed for this purpose. Here we demonstrate the application of nuclear magnetic resonance (NMR) spectroscopy and pair distribution function (PDF) analysis as new tools to probe the local structures of porous carbons, alongside more conventional Raman spectroscopy. Together, the PDFs and the Raman spectra allow the local chemical bonding to be probed, with the bonding becoming more ordered for carbide-derived carbons (CDCs) synthesized at higher temperatures. The ring currents induced in the NMR experiment (and thus the observed NMR chemical shifts for adsorbed species) are strongly dependent on the size of the aromatic carbon domains. We exploit this property and use computer simulations to show that the carbon domain size increases with the temperature used in the carbon synthesis. The techniques developed here are applicable to a wide range of porous carbons and offer new insights into the structures of CDCs (conventional and vacuum-annealed) and coconut shell-derived activated carbons.A.C.F., J.M.G., C.M., P.K.A, E.K.H., and C.P.G. acknowledge the Sims Scholarship (A.C.F.), EPSRC (via the Supergen consortium, J.M.G.), and the EU ERC (via an Advanced Fellowship to C.P.G.) for funding. C.M. and P.K.A. acknowledge the School of the Physical Sciences of the University of Cambridge for funding through an Oppenheimer Research Fellowship. P.K.A. acknowledges a Junior Research Fellowship from Gonville and Caius College, Cambridge. A.C.F. and J.M.G. thank the NanoDTC Cambridge for travel funding. M.A., M.Z., and V.P. acknowledge funding from the German Federal Ministry for Research and Education (BMBF) in support of the nanoEES3D project (Award Number 03EK3013) as part of the strategic funding initiative energy storage framework and kindly thank Prof. Arzt (INM) for his continuing support. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. We thank Daan Frenkel for his contributions to this work and Boris Dyatkin for comments on the manuscript.This is the author accepted manuscript. The final version is available from the American Chemical Society via http://dx.doi.org/10.1021/acs.chemmater.5b0321

NMR Study of Ion Dynamics and Charge Storage in Ionic Liquid Supercapacitors.

Ionic liquids are emerging as promising new electrolytes for supercapacitors. While their higher operating voltages allow the storage of more energy than organic electrolytes, they cannot currently compete in terms of power performance. More fundamental studies of the mechanism and dynamics of charge storage are required to facilitate the development and application of these materials. Here we demonstrate the application of nuclear magnetic resonance spectroscopy to study the structure and dynamics of ionic liquids confined in porous carbon electrodes. The measurements reveal that ionic liquids spontaneously wet the carbon micropores in the absence of any applied potential and that on application of a potential supercapacitor charging takes place by adsorption of counterions and desorption of co-ions from the pores. We find that adsorption and desorption of anions surprisingly plays a more dominant role than that of the cations. Having elucidated the charging mechanism, we go on to study the factors that affect the rate of ionic diffusion in the carbon micropores in an effort to understand supercapacitor charging dynamics. We show that the line shape of the resonance arising from adsorbed ions is a sensitive probe of their effective diffusion rate, which is found to depend on the ionic liquid studied, as well as the presence of any solvent additives. Taken as whole, our NMR measurements allow us to rationalize the power performances of different electrolytes in supercapacitors.A.C.F., J.M.G., C.M., P.M.B., H.W., and C.P.G. acknowledge the Sims Scholarship (A.C.F), EPSRC (via the Supergen consortium, J.M.G.), The School of Physical Sciences (University of Cambridge) for funding through an Oppen- heimer Research Fellowship (C.M.), The Marie Curie FP7 International Incoming Fellowship (P.M.B.), and the EU ERC (via an Advanced Fellowship to C.P.G.) for funding. A.C.F. and J.M.G. thank the NanoDTC Cambridge for travel funding. P.S. acknowledges support from the European Research Council (ERC, Advanced Grant, ERC-2011-AdG, Project 291543−IONACES).This is the final version. It first appeared at http://pubs.acs.org/doi/abs/10.1021/jacs.5b03958

Amine Dynamics in Diamine-Appended Mg2(dobpdc) Metal-Organic Frameworks.

Variable-temperature 15N solid-state NMR spectroscopy is used to uncover the dynamics of three diamines appended to the metal-organic framework Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate), an important family of CO2 capture materials. The results imply both bound and free amine nitrogen environments exist when diamines are coordinated to the framework open Mg2+ sites. There are rapid exchanges between two nitrogen environments for all three diamines, the rates and energetics of which are quantified by 15N solid-state NMR data and corroborated by density functional theory calculations and molecular dynamics simulations. The activation energy for the exchange provides a measure of the metal-amine bond strength. The unexpected negative correlation between the metal-amine bond strength and CO2 adsorption step pressure reveals that metal-amine bond strength is not the only important factor in determining the CO2 adsorption properties of diamine-appended Mg2(dobpdc) metal-organic frameworks

In Situ NMR Spectroscopy of Supercapacitors: Insight into the Charge Storage Mechanism

Electrochemical capacitors, commonly known as supercapacitors, are important energy storage devices with high power capabilities and long cycle lives. Here we report the development and application of in situ nuclear magnetic resonance(NMR) methodologies to study changes at the electrode−electrolyte interface in working devices as they charge and discharge. For a supercapacitor comprising activated carbon electrodes and an organic electrolyte, NMR experiments carried out at different charge states allow quantification of the number of charge storing species and show that there are at least two distinct charge storage regimes. At cell voltages below 0.75 V, electrolyte anions are increasingly desorbed from the carbon micropores at the negative electrode, while at the positive electrode there is little change in the number of anions that are adsorbed as the voltage is increased. However, above a cell voltage of 0.75 V, dramatic increases in the amount of adsorbed anions in the positive electrode are observed while anions continue to be desorbed at the negative electrode. NMR experiments with simultaneous cyclic voltammetry show that supercapacitor charging causes marked changes to the local environments of charge storing species, with periodic changes of their chemical shift observed. NMR calculations on a model carbon fragment show that the addition and removal of electrons from a delocalized system should lead to considerable increases in the nucleus-independent chemical shift of nearby species, in agreement with our experimental observations

Advance equitable livelihoods

Food system transformation provides the opportunity to shift current trends in all forms of malnutrition, prioritizing the availability and affordability of nutritious food for all – from shifting priorities in agricultural production, to improved food systems that favor nutrition and sustainability. The task of Action Track 4 is to explore approaches to doing so that will advance equitable livelihoods for producers, businesses, workers across the food system and consumers, with a particular emphasis on addressing inequalities and power imbalances. As the Science Group for AT 4, we explore the nature of these issues, using the drivers of food systems as articulated by the High Level Panel of Experts of the UN Committee on World Food Security (HLPE 2020) as framing. Small and medium-sized producers and people who rely on food systems in rural and urban areas for livelihoods are disproportionately affected by all biophysical and environmental drivers, including soil and water resources and climate change. Unequal opportunity in access to all types of resources reduces overall production, resilience and rural transformation. Advances in innovation, technology and infrastructure have had important impacts on food production and sustainability, transportation and processing along food value chains, marketing, and, ultimately, diets, including the consumption of both nutritious and unhealthy foods. However, achievement of equitable livelihoods in food systems will require that issues of access to contextually suitable innovation and technology, inclusive of indigenous knowledge, be substantially enhanced. Many economic and political factors can be essential causes of inequality and power imbalances at the household, community, national and global levels, which may constrain the ability of food system transformation to deliver poverty reduction and sustainable, equitable livelihoods. Finally, vast evidence illustrates that several socio-cultural and demographic drivers underpin inequalities among and within societies and constrain the potential for some to benefit from actions to improve their livelihoods, particularly women, youths, the disabled, the elderly and indigenous peoples. These issues have been exacerbated by the COVID-19 pandemic. The pandemic is having a significant impact on global commodity markets and trading systems, economic growth, incomes, and poverty levels, with a likely disproportionate burden falling on vulnerable communities in both urban and rural areas. This is likely to worsen inequalities and set back progress against poverty and hunger goals. To address these issues, we must transform not only food systems, but the structures and systems that continue to enable and exacerbate inequities. Drivers of food system inequities are highly interconnected, and progress in addressing one will likely require change across several. For example, globalization and trade interact with other powerful drivers, especially technology resource mobilization and demographic trends, which shape food production, distribution, and consumption. Hence, in the final section, we reflect on several factors that should be part of effective solutions for combating inequalities in food systems, including rights-based approaches. We then share a series of recommendations aimed at enhancing inclusive decision-making, protecting the livelihoods of those living in situations of vulnerability while creating opportunities, adapting institutions and policies to favor equitable food system livelihoods, and increasing investment so as to realize the potential of improved institutional and policy actions. We invite governments, businesses, and organizations to hold themselves and others to account in advancing equitable livelihoods, and open avenues towards realizing the potential of science, innovation, technology, and evidence to favor equitable livelihoods

Ring current effects: Factors affecting the NMR chemical shift of molecules adsorbed on porous carbons

Nuclear magnetic resonance (NMR) spectroscopy is increasingly being used to study the adsorption of molecules in porous carbons, a process which underpins applications ranging from electrochemical energy storage to water purification. Here we present density functional theory (DFT) calculations of the nucleus-independent chemical shift (NICS) near various sp2-hybridized carbon fragments to explore the structural factors that may affect the resonance frequencies observed for adsorbed species. The domain size of the delocalized electron system affects the calculated NICSs, with larger domains giving rise to larger chemical shieldings. In slit pores, overlap of the ring current effects from the pore walls is shown to increase the chemical shielding. Finally, curvature in the carbon sheets is shown to have a significant effect on the NICS. The trends observed are consistent with existing NMR results as well as new spectra presented for an electrolyte adsorbed on carbide-derived carbons prepared at different temperatures