A Neutron Diffraction Study of the Electrochemical Double Layer Capacitor Electrolyte Tetrapropylammonium Bromide in Acetonitrile.

Neutron diffraction with isotopic substitution has been used to characterize the bulk liquid structure of the technologically relevant electrolyte solution, 1 M tetrapropylammonium bromide (TPA Br) in acetonitrile (acn), and of pure deuterated acetonitrile. Empirical potential structure refinement modeling procedures have been used to extract detailed structural information about solvent-solvent, solvent-ion, and ion-ion correlations. Analysis of the refined data shows the expected local dipolar conformation of acn in the pure solvent. This short-range dipolar ordering is also present within the solutions of TPA Br in acn, and it affects how the solvent orders itself around the ions. The solvation numbers of the TPA cations and the bromide anions are deduced, 8 and 5, respectively, as are the orientations of the solvent molecules that surround the ions. Evidence for ion association is also presented, with nearly two-thirds of the ions in the system being in associated pairs or clusters.E.K.H. acknowledges the European Research Council ERC Grant ERC-2009-AdG-247411 for funding. P.K.A acknowledges a Junior Research Fellowship from Gonville and Caius College, an Oppenheimer Fellowship from the University of Cambridge. R.J.L.W. acknowledges the EPSRC Grant 11220426 for funding.This is the author accepted manuscript. The final version is available from ACS via http://dx.doi.org/10.1021/acs.jpcb.5b0824

Suppression of self-discharge in a non-flowing bromine battery via <i>in situ </i>generation of countercharged groups

Bromine is attractive for next-generation energy-storage systems because of its high capacity and natural abundance. However, because of issues relating to self-discharging processes, prototypes involving bromide/bromine redox couples are largely limited to the design of flow cells. Here we propose a method to exploit bromine redox chemistry and demonstrate the feasibility of mitigating ion depletion in a stationary device. A cell using polyaniline vapor-grown carbon fiber (PANI-VGCF) as the electrode material exhibits close to 100% Coulombic efficiency at a low current density (50 mA/g). Electrochemical results, operando Raman spectroscopy, and theoretical analysis provide clues that the strong interaction between protonated PANI and Br−/ Br3− makes their decoupling unfavorable, thereby suppressing self-discharge processes. This strategy could be utilized for rational design of other conjugated materials/bromine systems without self-discharge issues

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

Research data supporting the publication "Under Pressure: Offering Fundamental Insight into Structural Changes on Ball Milling Battery Materials"

Data depository includes the following: Powder X-ray diffraction (PXRD) of the ball-milled Li2MoO4 (at 40Hz and 50Hz, with varying ball size of 7 and 10 mm). PXRD of H-Nb2O5 ball-milled at 40 Hz and 50 Hz (7 mm ball) Electrochemical data of Li2MoO4 and Li2MnO3 (ball-milled samples). TEM of Li2MoO4 and the ball-milled equivalent. Li and Mo NMR of Li2MoO4 and the ball-milled equivalent

A radially accessible tubular in situ X-ray cell for spatially resolved operando scattering and spectroscopic studies of electrochemical energy storage devices

A tubular operando electrochemical cell has been developed to allow spatially resolved X-ray scattering and spectroscopic measurements of individual cell components, or regions thereof, during device operation. These measurements are enabled by the tubular cell geometry, wherein the X-ray-transparent tube walls allow radial access for the incident and scattered/transmitted X-ray beam; by probing different depths within the electrode stack, the transformation of different components or regions can be resolved. The cell is compatible with a variety of synchrotron-based scattering, absorption and imaging methodologies. The reliability of the electrochemical cell and the quality of the resulting X-ray scattering and spectroscopic data are demonstrated for two types of energy storage: the evolution of the distribution of the state of charge of an Li-ion battery electrode during cycling is documented using X-ray powder diffraction, and the redistribution of ions between two porous carbon electrodes in an electrochemical double-layer capacitor is documented using X-ray absorption near-edge spectroscopy

In situ studies of materials for high temperature CO2 capture and storage.

Carbon capture and storage (CCS) offers a possible solution to curb the CO2 emissions from stationary sources in the coming decades, considering the delays in shifting energy generation to carbon neutral sources such as wind, solar and biomass. The most mature technology for post-combustion capture uses a liquid sorbent, amine scrubbing. However, with the existing technology, a large amount of heat is required for the regeneration of the liquid sorbent, which introduces a substantial energy penalty. The use of alternative sorbents for CO2 capture, such as the CaO-CaCO3 system, has been investigated extensively in recent years. However there are significant problems associated with the use of CaO based sorbents, the most challenging one being the deactivation of the sorbent material. When sorbents such as natural limestone are used, the capture capacity of the solid sorbent can fall by as much as 90 mol% after the first 20 carbonation-regeneration cycles. In this study a variety of techniques were employed to understand better the cause of this deterioration from both a structural and morphological standpoint. X-ray and neutron PDF studies were employed to understand better the local surface and interfacial structures formed upon reaction, finding that after carbonation the surface roughness is decreased for CaO. In situ synchrotron X-ray diffraction studies showed that carbonation with added steam leads to a faster and more complete conversion of CaO than under conditions without steam, as evidenced by the phases seen at different depths within the sample. Finally, in situ X-ray tomography experiments were employed to track the morphological changes in the sorbents during carbonation, observing directly the reduction in porosity and increase in tortuosity of the pore network over multiple calcination reactions.M.T. Dunstan acknowledges funding from the Cambridge Commonwealth Trusts and Trinity College, Cambridge. M.T. Dunstan, S.A. Scott, J.S. Dennis and C.P. Grey acknowledge funding from EPSRC Grant No. EP/K030132/1. W. Liu acknowledges funding from NRF, Singapore under its CREATE programme. The authors would like to thank the Science Facilities and Technologies Council, Diamond Light Source and Paul Scherrer Institut for the award of beamtime. The authors would especially like to thank Dr Julie Fife and Dr David Haberthür at TOMCAT, Dr Tristan Youngs and Dr Daniel Bowron at NIMROD, and Dr Philip Chater at I15 for their assistance in collecting and processing the data, and Simon Griggs for assistance with SEM. M.W. Gaultois is grateful for support from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No. 659764.This is the author accepted manuscript. The final version is available from the Royal Society of Chemistry via http://dx.doi.org/10.1039/C6FD00047

The effectiveness, implementation, and experiences of peer support approaches for mental health: A systematic umbrella review

Background: Peer support for mental health is recommended across international policy guidance and provision. Our systematic umbrella review summarises evidence on the effectiveness, implementation, and experiences of paid peer support approaches for mental health. Methods: We searched MEDLINE, EMBASE, PsycINFO, The Campbell Collaboration, and The Cochrane Database of Systematic Reviews (2012–2022) for reviews of paid peer support interventions for mental health. The AMSTAR2 assessed quality. Results were synthesised narratively, with implementation reported using the CFIR (Consolidated Framework for Implementation Research). The protocol was registered with PROSPERO (registration number: CRD42022362099). Results: We included 35 reviews (426 primary studies, n = 95–40,927 participants): systematic reviews with (n = 13) or without (n = 13) meta-analysis, or with qualitative synthesis (n = 3), scoping reviews (n = 6). Most reviews were low or critically low (97%) quality, one review was high quality. Effectiveness was investigated in 23 reviews. Results were mixed; there was some evidence from meta-analyses that peer support may improve depression symptoms (particularly perinatal depression), self-efficacy, and recovery. Factors promoting successful implementation, investigated in 9 reviews, included adequate training and supervision, a recovery-oriented workplace, strong leadership, and a supportive and trusting workplace culture with effective collaboration. Barriers included lack of time, resources and funding, and lack of recognised peer support worker (PSW) certification. Experiences of peer support were explored in 11 reviews, with 3 overarching themes: (i) what the PSW role can bring, including recovery and improved wellbeing for service users and PSWs; (ii) confusion over the PSW role, including role ambiguity and unclear boundaries; and (iii) organisational challenges and impact, including low pay, negative non-peer staff attitudes, and lack of support and training. Conclusions: Peer support may be effective at improving some clinical outcomes, self-efficacy, and recovery. Certain populations, e.g. perinatal populations, may especially benefit from peer support. Potential strategies to successfully implement PSWs include co-production, clearly defined PSW roles, a receptive hierarchical structure and staff, appropriate PSW and staff training with clinical and/or peer supervision alongside safeguarding. Services could benefit from clear, coproduced, setting specific implementation guidelines for PSW. PSW roles tend to be poorly defined and associations between PSW intervention content and impacts need further investigation. Future research should reflect the priorities of providers/service users involved in peer support

Synthesis and structural characterization of a single-crystal to single-crystal transformable coordination polymer

A single-crystal to single-crystal transformable coordination polymer compound was hydrothermally synthesized. The structural rearrangement is induced by selecting a ligand that contains both strong and weaker coordinating groups. Both hydrated and dehydrated structures were determined by single crystal X-ray analysis.PostprintPeer reviewe