Showing papers on "Ion published in 2021"

Science Requirements and Detector Concepts for the Electron-Ion Collider: EIC Yellow Report

Abstract: This report describes the physics case, the resulting detector requirements, and the evolving detector concepts for the experimental program at the Electron-Ion Collider (EIC). The EIC will be a powerful new high-luminosity facility in the United States with the capability to collide high-energy electron beams with high-energy proton and ion beams, providing access to those regions in the nucleon and nuclei where their structure is dominated by gluons. Moreover, polarized beams in the EIC will give unprecedented access to the spatial and spin structure of the proton, neutron, and light ions. The studies leading to this document were commissioned and organized by the EIC User Group with the objective of advancing the state and detail of the physics program and developing detector concepts that meet the emerging requirements in preparation for the realization of the EIC. The effort aims to provide the basis for further development of concepts for experimental equipment best suited for the science needs, including the importance of two complementary detectors and interaction regions. This report consists of three volumes. Volume I is an executive summary of our findings and developed concepts. In Volume II we describe studies of a wide range of physics measurements and the emerging requirements on detector acceptance and performance. Volume III discusses general-purpose detector concepts and the underlying technologies to meet the physics requirements. These considerations will form the basis for a world-class experimental program that aims to increase our understanding of the fundamental structure of all visible matter

Copper-coordinated cellulose ion conductors for solid-state batteries.

Abstract: Although solid-state lithium (Li)-metal batteries promise both high energy density and safety, existing solid ion conductors fail to satisfy the rigorous requirements of battery operations. Inorganic ion conductors allow fast ion transport, but their rigid and brittle nature prevents good interfacial contact with electrodes. Conversely, polymer ion conductors that are Li-metal-stable usually provide better interfacial compatibility and mechanical tolerance, but typically suffer from inferior ionic conductivity owing to the coupling of the ion transport with the motion of the polymer chains1–3. Here we report a general strategy for achieving high-performance solid polymer ion conductors by engineering of molecular channels. Through the coordination of copper ions (Cu2+) with one-dimensional cellulose nanofibrils, we show that the opening of molecular channels within the normally ion-insulating cellulose enables rapid transport of Li+ ions along the polymer chains. In addition to high Li+ conductivity (1.5 × 10−3 siemens per centimetre at room temperature along the molecular chain direction), the Cu2+-coordinated cellulose ion conductor also exhibits a high transference number (0.78, compared with 0.2–0.5 in other polymers2) and a wide window of electrochemical stability (0–4.5 volts) that can accommodate both the Li-metal anode and high-voltage cathodes. This one-dimensional ion conductor also allows ion percolation in thick LiFePO4 solid-state cathodes for application in batteries with a high energy density. Furthermore, we have verified the universality of this molecular-channel engineering approach with other polymers and cations, achieving similarly high conductivities, with implications that could go beyond safe, high-performance solid-state batteries. By coordinating copper ions with the oxygen-containing groups of cellulose nanofibrils, the molecular spacing in the nanofibrils is increased, allowing fast transport of lithium ions and offering hopes for solid-state batteries.

Revealing Charge Carrier Mobility and Defect Densities in Metal Halide Perovskites via Space-Charge-Limited Current Measurements

Abstract: Space-charge-limited current (SCLC) measurements have been widely used to study the charge carrier mobility and trap density in semiconductors. However, their applicability to metal halide perovskites is not straightforward, due to the mixed ionic and electronic nature of these materials. Here, we discuss the pitfalls of SCLC for perovskite semiconductors, and especially the effect of mobile ions. We show, using drift-diffusion (DD) simulations, that the ions strongly affect the measurement and that the usual analysis and interpretation of SCLC need to be refined. We highlight that the trap density and mobility cannot be directly quantified using classical methods. We discuss the advantages of pulsed SCLC for obtaining reliable data with minimal influence of the ionic motion. We then show that fitting the pulsed SCLC with DD modeling is a reliable method for extracting mobility, trap, and ion densities simultaneously. As a proof of concept, we obtain a trap density of 1.3 × 1013 cm-3, an ion density of 1.1 × 1013 cm-3, and a mobility of 13 cm2 V-1 s-1 for a MAPbBr3 single crystal.

Novel Lamellar Tetrapotassium Pyromellitic Organic for Robust High-Capacity Potassium Storage.

Abstract: Redox-active organics are investigation hotspots for metal ion storage due to their structural diversity and redox reversibility. However, they are plagued by limited storage capacity, sluggish ion diffusion kinetics, and weak structural stability, especially for K+ ion storage. Herein, we firstly reported the lamellar tetrapotassium pyromellitic (K4 PM) with four active sites and large interlayer distance for K+ ion storage based on a design strategy, where organics are constructed with the small molecular mass, multiple active sites, fast ion diffusion channels, and rigid conjugated π bonds. The K4 PM electrode delivers a high capacity up to 292 mAh g-1 at 50 mA g-1 , among the best reported organics for K+ ion storage. Especially, it achieves an excellent rate capacity and long-term cycling stability with a capacity retention of ≈83 % after 1000 cycles. Incorporating in situ and ex-situ techniques, the K+ ion storage mechanism is revealed, where conjugated carboxyls are reversibly rearranged into enolates to stably store K+ ions. This work sheds light on the rational design and optimization of organic electrodes for efficient metal ion storage.

Efficient Ion Sieving in Covalent Organic Framework Membranes with Sub-2-Nanometer Channels.

Abstract: Membranes of sub-2-nanometer channels show high ion transport rates, but it remains a great challenge to design such membranes with desirable ion selectivities for ion separation applications. Here, covalent organic framework (COF) membranes with a channel size of ≈1.4 nm and abundant hydrogen bonding sites, exhibiting efficient ion sieving properties are demonstrated. The COF membranes have high monovalent cation permeation rates of 0.1-0.2 mol m-2 h-1 and extremely low multivalent cation permeabilities, leading to high monovalent over divalent ion selectivities for K+ /Mg2+ of ≈765, Na+ /Mg2+ of ≈680, and Li+ /Mg2+ of ≈217. Experimental measurements and theoretical simulations reveal that the hydrogen bonding interaction between hydrated cations and the COF channel wall governs the high selectivity, and divalent cations transport through the channel needs to overcome higher energy barriers than monovalent cations. These findings provide an effective strategy for developing sub-2-nanometer sized membranes with specific interaction sites for high-efficiency ionic separation.

Designing Biomimic Two-Dimensional Ionic Transport Channels for Efficient Ion Sieving

Abstract: Ion transport is crucial for biological systems and membrane-based technologies from both fundamental and practical aspects. Unlike biological ion channels, realizing efficient ion sieving by using membranes with artificial ion channels remains an extremely challenging task. Inspired by biological ion channels with proper steric containment of target ions within affinitive binding sites along the selective filter, herein we design a system of biomimic two-dimensional (2D) ionic transport channels based on a graphene oxide (GO) membrane, where the ionic imidazole group tunes the appropriate physical confinement of 2D ionic transport channels to mimic the confined cavity structures of the biological selectivity filter, and the ionic sulfonic group creates a favorable chemical environment of 2D ionic transport channels to mimic the affinitive binding sites of the biological selectivity filter. As a result, the as-fabricated ionic GO membrane demonstrates an exceptional K+ transport rate of ∼1.36 mol m-2 h-1 and competitive K+/Mg2+ selectivity of ∼9.11, outperforming state-of-the-art counterparts. Moreover, the semiquantitative studies of ion transport through 2D ionic transport channels suggest that efficient ion sieving with the ionic GO membrane is achieved by the high diffusion and partition coefficients of hydrated monovalent ions, as well as the large energy barrier and limited potential gradient of hydrated divalent ions encountered.

Atomic-scale ion transistor with ultrahigh diffusivity

Abstract: Biological ion channels rapidly and selectively gate ion transport through atomic-scale filters to maintain vital life functions. We report an atomic-scale ion transistor exhibiting ultrafast and highly selective ion transport controlled by electrical gating in graphene channels around 3 angstroms in height, made from a single flake of reduced graphene oxide. The ion diffusion coefficient reaches two orders of magnitude higher than the coefficient in bulk water. Atomic-scale ion transport shows a threshold behavior due to the critical energy barrier for hydrated ion insertion. Our in situ optical measurements suggest that ultrafast ion transport likely originates from highly dense packing of ions and their concerted movement inside the graphene channels.

High content anion (S/Se/P) doping assisted by defect engineering with fast charge transfer kinetics for high-performance sodium ion capacitors

Abstract: The rate-determining process for sodium storage in TiO2 is greatly depending on charge transfer happening in the electrode materials owing to its inferior diffusion coefficient and electronic conductivity. Apart from reducing the diffusion distance of ion/electron, the increasement of ionic/electronic mobility in the crystal lattice is also very important for charge transport. Here, an oxygen vacancy (OV) engineering assisted in high-content anion (S/Se/P) doping strategy to enhance charge transfer kinetics for ultrafast sodium-storage performance is proposed. Theoretical calculations indicate that OV-engineering evokes spontaneous S doping into the TiO2 phase and achieves high dopant concentration to bring about impurity state electron donor and electronic delocalization over S occupied sites, which can largely reduce the migration barrier of Na+. To realize the speculation, high-content anion doped anatase TiO2/C composites (9.82 at% for S in A-TiO2–x-S/C) are elaborately designed. The optimized A-TiO2–x-S/C anode exhibits extraordinarily high-rate capability with 209.6 mAh g−1 at 5000 mA g−1. The assembled sodium ion capacitors deliver an ultrahigh energy density of 150.1 Wh kg−1 at a power density of 150 W kg−1 when applied as anode materials. This work provides a new strategy to realize high content anion doping concentration, and enhances the charge transfer kinetics for TiO2, which delivers an efficient approach for the design of electrode materials with fast kinetic.

In Situ Characterization of Dehydration during Ion Transport in Polymeric Nanochannels.

Abstract: The transport of hydrated ions across nanochannels is central to biological systems and membrane-based applications, yet little is known about their hydrated structure during transport due to the absence of in situ characterization techniques. Herein, we report experimentally resolved ion dehydration during transmembrane transport using modified in situ liquid ToF-SIMS in combination with MD simulations for a mechanistic reasoning. Notably, complete dehydration was not necessary for transport to occur across membranes with sub-nanometer pores. Partial shedding of water molecules from ion solvation shells, observed as a decrease in the average hydration number, allowed the alkali-metal ions studied here (lithium, sodium, and potassium) to permeate membranes with pores smaller than their solvated size. We find that ions generally cannot hold more than two water molecules during this sterically limited transport. In nanopores larger than the size of the solvation shell, we show that ionic mobility governs the ion hydration number distribution. Viscous effects, such as interactions with carboxyl groups inside the membrane, preferentially hinder the transport of the mono- and dihydrates. Our novel technique for studying ion solvation in situ represents a significant technological leap for the nanofluidics field and may enable important advances in ion separation, biosensing, and battery applications.

Measuring the α-particle charge radius with muonic helium-4 ions

Abstract: The energy levels of hydrogen-like atomic systems can be calculated with great precision. Starting from their quantum mechanical solution, they have been refined over the years to include the electron spin, the relativistic and quantum field effects, and tiny energy shifts related to the complex structure of the nucleus. These energy shifts caused by the nuclear structure are vastly magnified in hydrogen-like systems formed by a negative muon and a nucleus, so spectroscopy of these muonic ions can be used to investigate the nuclear structure with high precision. Here we present the measurement of two 2S–2P transitions in the muonic helium-4 ion that yields a precise determination of the root-mean-square charge radius of the α particle of 1.67824(83) femtometres. This determination from atomic spectroscopy is in excellent agreement with the value from electron scattering1, but a factor of 4.8 more precise, providing a benchmark for few-nucleon theories, lattice quantum chromodynamics and electron scattering. This agreement also constrains several beyond-standard-model theories proposed to explain the proton-radius puzzle2–5, in line with recent determinations of the proton charge radius6–9, and establishes spectroscopy of light muonic atoms and ions as a precise tool for studies of nuclear properties. The 2S–2P transitions in muonic helium-4 ions are measured using laser spectroscopy and used to obtain an α-particle charge-radius value five times more precise than that from electron scattering.

Constructing Uranyl-Specific Nanofluidic Channels for Unipolar Ionic Transport to Realize Ultrafast Uranium Extraction.

Abstract: High-speed capturing of uranyl (UO22+) ions from seawater elicits unprecedented interest for the sustainable development of the nuclear energy industry. However, the ultralow concentration (∼3.3 μg L-1) of uranium element leads to the slow ion diffusion inside the adsorbent particle, especially after the transfer paths are occupied by the coexisted interfering ions. Considering the geometric dimension of UO22+ ion (a maximum length of 6.04-6.84 A), the interlayer spacing of graphene sheets was covalently pillared with phenyl-based units into twice the ionic length (13 A) to obtain uranyl-specific nanofluidic channels. Applying a negative potential (-1.3 V), such a charge-governed region facilitates a unipolar ionic transport, where cations are greatly accelerated and co-ions are repelled. Notably, the resulting adsorbent gives the highest adsorption velocity among all reported materials. The adsorption capacity measured after 56 days of exposure in natural seawater is evaluated to be ∼16 mg g-1. This novel concept with rapid adsorption, high capacity, and facile operating process shows great promise to implement in real-world uranium extraction.

Carbon Dots Evoked Li Ion Dynamics for Solid State Battery.

Abstract: Solid composite electrolyte-based Li battery is viewed as one of the most competitive system for the next generation batteries; however, it is still restricted by sluggish ion diffusion. Fast ion transport is a characteristic of the polyethylene oxide (PEO) amorphous phase, and the mobility of Li+ is restrained by the coordination interaction within PEO and Li+ . Herein, the design of applying functionalized carbon dots (CDs) with abundant surface features as fillers is proposed. High ionic conductivity is achieved in the CD-based composite electrolytes resulting from enhanced ion migration ability of polymer segments and mobility of Li+ . Specially, the optimum effect with nitrogen and sulfur co-doped carbon dots (NS-CD) is a consequence of strong interaction between edge-nitrogen/sulfur in NS-CD and Li+ . Solid-state nuclear magnetic resonance results confirm that more mobile Li+ is generated. Moreover, it is observed that lithium dendrite is suppressed compared to PEO electrolyte associated with reinforced mechanical properties and high transference number. The corresponding all-solid-state batteries, with the cathode of LiFePO4 or high voltage NCM523, exhibit long cycling life and excellent rate performances. It is a novel strategy to achieve high ionic conductivity composite electrolyte with uniform lithium deposition and provides a new direction to the mechanism of fast Li+ movement.

Parameterization of Monovalent Ions for the OPC3, OPC, TIP3P-FB, and TIP4P-FB Water Models.

Abstract: Monovalent ions play significant roles in various biological and material systems Recently, four new water models (OPC3, OPC, TIP3P-FB, and TIP4P-FB), with significantly improved descriptions of condensed phase water, have been developed The pairwise interaction between the metal ion and water necessitates the development of ion parameters specifically for these water models Herein, we parameterized the 12-6 and the 12-6-4 nonbonded models for 12 monovalent ions with the respective four new water models These monovalent ions contain eight cations including alkali metal ions (Li+, Na+, K+, Rb+, Cs+), transition-metal ions (Cu+ and Ag+), and Tl+ from the boron family, along with four halide anions (F-, Cl-, Br-, I-) Our parameters were designed to reproduce the target hydration free energies (the 12-6 hydration free energy (HFE) set), the ion-oxygen distances (the 12-6 ion-oxygen distance (IOD) set), or both of them (the 12-6-4 set) The 12-6-4 parameter set provides highly accurate structural features overcoming the limitations of the routinely used 12-6 nonbonded model for ions Specifically, we note that the 12-6-4 parameter set is able to reproduce experimental hydration free energies within 1 kcal/mol and experimental ion-oxygen distances within 001 A simultaneously We further reproduced the experimentally determined activity derivatives for salt solutions, validating the ion parameters for simulations of ion pairs The improved performance of the present water models over our previous parameter sets for the TIP3P, TIP4P, and SPC/E water models (Li, P et al J Chem Theory Comput 2015 11 1645 1657) highlights the importance of the choice of water model in conjunction with the metal ion parameter set

Ultraselective Monovalent Metal Ion Conduction in a Three-Dimensional Sub-1 nm Nanofluidic Device Constructed by Metal–Organic Frameworks

Abstract: Construction of nanofluidic devices with an ultimate ion selectivity analogue to biological ion channels has been of great interest for their versatile applications in energy harvesting and conversion, mineral extraction, and ion separation. Herein, we report a three-dimensional (3D) sub-1 nm nanofluidic device to achieve high monovalent metal ion selectivity and conductivity. The 3D nanofluidic channel is constructed by assembly of a carboxyl-functionalized metal-organic framework (MOF, UiO-66-COOH) crystals with subnanometer pores into an ethanediamine-functionalized polymer nanochannel via a nanoconfined interfacial growth method. The 3D UiO-66-COOH nanofluidic channel achieves an ultrahigh K+/Mg2+ selectivity up to 1554.9, and the corresponding K+ conductivity is one to three orders of magnitude higher than that in bulk. Drift-diffusion experiments of the nanofluidic channel further reveal an ultrahigh charge selectivity (K+/Cl-) up to 112.1, as verified by the high K/Cl content ratio in UiO-66-COOH. The high metal ion selectivity is attributed to the size-exclusion, charge selectivity, and ion binding of the negatively charged MOF channels. This work will inspire the design of diverse MOF-based nanofluidic devices for ultimate ion separation and energy conversion.