Anionic Carriers Research Articles

Non-Metal Ion Storage in Zinc-Organic Batteries.

Zinc-organic batteries (ZOBs) are receiving widespread attention as up-and-coming energy-storage systems due to their sustainability, operational safety and low cost. Charge carrier is one of the critical factors affecting the redox kinetics and electrochemical performances of ZOBs. Compared with conventional large-sized and sluggish Zn2+ storage, non-metallic charge carriers with small hydrated size and light weight show accelerated interfacial dehydration and fast reaction kinetics, enabling superior electrochemical metrics for ZOBs. Thus, it is valuable and ongoing works to build better ZOBs with non-metallic ion storage. In this review, versatile non-metallic cationic (H+, NH4 +) and anionic (Cl-, OH-, CF3SO3 -, SO4 2-) charge carriers of ZOBs are first categorized with a brief comparison of their respective physicochemical properties and chemical interactions with redox-active organic materials. Furthermore, this work highlights the implementation effectiveness of non-metallic ions in ZOBs, giving insights into the impact of ion types on the metrics (capacity, rate capability, operation voltage, and cycle life) of organic cathodes. Finally, the challenges and perspectives of non-metal-ion-based ZOBs are outlined to guild the future development of next-generation energy communities.

The Effect of Anionic and Cationic Charge Carriers on the Supercapacitive Behavior of Graphene Nanoribbons

As worldwide energy consumption continues to increase, so too does the demand for improved energy storage technologies. Supercapacitors have attracted a lot of attention due to their quick charging/discharging rate, high power density, and long-term cycling stability in comparison to conventional batteries.1 Graphene nanoribbons (GNRs) with ultrathin two-dimensional structures and unique properties received a lot of attention recently as potential materials for electrochemical energy storage and specifically supercapacitors.2,3 GNRs maintain graphene’s unique lattice structure in one dimension and provide more open-edge structures compared to graphene, thus allowing faster ion diffusion, which makes GNRs highly promising for energy storage systems.2,3 GNRs have unique characteristics such as exceptional electrical conductivity, a highly modifiable surface area, strong chemical stability, low toxicity, great mechanical behavior, and the ability to tune properties for the desired application.This presentation provides an overview of the production of GNRs from carbon nanotubes and their application in supercapacitors. The physical/chemical structure of GNRs was evaluated using XRD, TEM, FT-IR, Raman spectroscopy, and XPS. Since the selection of the cation and anion has been reported to have a dramatic effect on the specific capacitance of the studied materials,4 the supercapacitive behavior of GNR was thoroughly investigated in various media (H2SO4, KOH, K2SO4 ), using different loadings and different evaluation systems (three and two-electrode systems). GNRs, in all of the tested media, showed good stability (retained 95% of their capacitance over 10,000 cycles at a high current density of 10 A/g), a wide potential window (up to 1.7 V), and a relatively high capacitance (≈ 400-800 F/g). The best medium for GNRs highest supercapacitance in correlation with their surface chemical structure will be discussed.

Ion Co-storage in Porous Organic Frameworks through On-site Coulomb Interactions for High Energy and Power Density Batteries.

Fast and continuous ion insertion is blocked in the common electrodes operating with widely accepted single-ion storage mechanism, primarily due to Coulomb repulsion between the same ions. It results in an irreconcilable conflict between capacity and rate performance. Herein, we designed a porous organic framework with novel multiple-ion co-storage modes, including PF6 - /Li+ , OTF- /Mg2+ , and OTF- /Zn2+ co-storage. The Coulomb interactions between cationic and anionic carriers in the framework can significantly promote electrode kinetics, by rejuvenating fast ion carrier migration toward framework interior. Consequently, the framework via PF6 - /Li+ co-storage mode shows a high energy density of 878 Wh kg-1 cycled more than 20 000 cycles, with an excellent power density of 28 kW kg-1 that is already comparable to commercial supercapacitors. The both greatly improved energy and power densities via the co-storage mode may pave a way for exploring new electrodes that are not available from common single-ion electrodes.

Ion Co‐storage in Porous Organic Frameworks through On‐site Coulomb Interactions for High Energy and Power Density Batteries

AbstractFast and continuous ion insertion is blocked in the common electrodes operating with widely accepted single‐ion storage mechanism, primarily due to Coulomb repulsion between the same ions. It results in an irreconcilable conflict between capacity and rate performance. Herein, we designed a porous organic framework with novel multiple‐ion co‐storage modes, including PF6−/Li+, OTF−/Mg2+, and OTF−/Zn2+ co‐storage. The Coulomb interactions between cationic and anionic carriers in the framework can significantly promote electrode kinetics, by rejuvenating fast ion carrier migration toward framework interior. Consequently, the framework via PF6−/Li+ co‐storage mode shows a high energy density of 878 Wh kg−1 cycled more than 20 000 cycles, with an excellent power density of 28 kW kg−1 that is already comparable to commercial supercapacitors. The both greatly improved energy and power densities via the co‐storage mode may pave a way for exploring new electrodes that are not available from common single‐ion electrodes.

Rechargeable aluminum-ion battery based on interface energy storage in two-dimensional layered graphene/TiO2 electrode

Rechargeable aluminum-ion batteries (AIBs) are expected to be one of the most concerned energy storage devices due to their high theoretical specific capacity, low cost, and high safety. At present, to explore the positive material with a high aluminum ion storage capability is an important factor in the development of high-performance AIBs. This paper proposes an AIB using two-dimensional layered graphene/TiO2 nanosheets composite as the highly reversible positive electrode and chloroaluminate ionic liquid as the electrolyte. AlCl4− and Al2Cl7− are proven to be the main anionic carriers in the charge storage. The AIBs exhibit excellent electrochemical performances in the voltage range of 0.1–0.9 V. A discharge specific capacity of 313.2 mAh/g at 0.1 A/g is achieved. Moreover, a high specific capacity of 40.0 mAh/g is still maintained at 1.0 A/g after 100 cycles. The superior electrochemical properties for the AIBs are attributed to the interfacial energy storage mechanism in the layered graphene/TiO2 nanosheets composite, providing the unique two-dimensional interface charge storage layer for the insertion/de-insertion of the AlxCly−. These meaningful results have important guiding significance for the development of high-performance AIBs.

Boron clusters as broadband membrane carriers

The membrane translocation of hydrophilic substances constitutes a challenge for their application as therapeutic compounds and labelling probes1–4. To remedy this, charged amphiphilic molecules have been classically used as carriers3,5. However, such amphiphilic carriers may cause aggregation and non-specific membrane lysis6,7. Here we show that globular dodecaborate clusters, and prominently B12Br122−, can function as anionic inorganic membrane carriers for a broad range of hydrophilic cargo molecules (with molecular mass of 146–4,500 Da). We show that cationic and neutral peptides, amino acids, neurotransmitters, vitamins, antibiotics and drugs can be carried across liposomal membranes. Mechanistic transport studies reveal that the carrier activity is related to the superchaotropic nature of these cluster anions8–12. We demonstrate that B12Br122− affects cytosolic uptake of different small bioactive molecules, including the antineoplastic monomethyl auristatin F, the proteolysis targeting chimera dBET1 and the phalloidin toxin, which has been successfully delivered in living cells for cytoskeleton labelling. We anticipate the broad and distinct delivery spectrum of our superchaotropic carriers to be the starting point of conceptually distinct cell-biological, neurobiological, physiological and pharmaceutical studies.

Synthesis and self-assembly of amphiphilic diblock polycarbonates with various pendant hydrophilic groups

Self-assembled micro-paricles have been proven to be efficient microcarriers for delivering various therapeutic agents. Polycarbonates have demonstrated excellent biodegradability and biocompatibility as material for polymeric microcarriers. A diblock polycarbonate with tunable block length and active sites is synthesized via one-pot sequential ring-opening polymerization (ROP). The polymer acts as a material platform for versatile modifications to prepare a series of amphiphilic diblock polycarbonates which can self-assemble into microparticles. The effect of different hydrophilic pendent groups controlling the morphology and surface charge of the assemblies is systematically investigated. The non-equilibrium spherical particles with varying sizes are formed in one day, and the spheres can further assemble into multi-compartments vesicles (MCVs). Cationic, anionic or neutral carriers can be prepared depending on the type of pendant groups attached. The versatile amphiphilic copolymer assemblies have good potential in biomedical applications.

A review of halide charge carriers for rocking‐chair and dual‐ion batteries

AbstractThis review discusses how halide ion species have been used as charge carriers in both anion rocking‐chair and dual‐ion battery (DIB) systems. The anion rocking‐chair batteries based on fluoride and chloride have emerged over the past decade and are garnering increased research interest due to their large theoretical energy density values and the natural abundance of halide‐containing materials. Moreover, DIBs that use halide species as their anionic charge carrier are seen as one of the promising next‐generation battery technologies due to their low cost and high working potentials. Although numerous polyatomic anions have been studied as charge carriers, the use of single halide ions (i.e., F− and Cl−) and metal‐based superhalides (e.g., [MgCl3]−) as anionic charge carriers in DIBs has been considerably less explored. Herein, we provide an overview of some of the key advances and recent progress that has been made with regard to halide ion charge carriers in electrochemical energy storage. We offer our perspectives on the current state of the field and provide a roadmap in hopes that it helps researchers toward making new advances in these promising and emerging areas.

Non-metallic charge carriers for aqueous batteries

Charge carriers are fundamental components of batteries that determine battery chemistry and performance. Non-metallic charge carriers provide an alternative to metallic charge carriers in aqueous batteries, enabling fast kinetics, long cyclic lifetime and low manufacturing costs. Non-metallic charge carriers not only can be inserted into the electrode framework, where they establish covalent–ionic bonds, but can also serve as reversible redox centres for charge transfer, resulting in superior performance compared with metallic charge carrier-based devices. In this Review, we discuss cationic and anionic non-metallic charge carriers, their physicochemical properties, charge storage mechanisms and electrode interactions. We examine battery configurations of non-metallic charge carrier-based devices and analyse battery performance based on costs, capacity, working potential, rate capability and cycling stability. Finally, we highlight design strategies for aqueous batteries based on non-metallic charge carriers and future applications. This Review discusses non-metallic charge carriers for aqueous batteries, investigating fundamental mechanisms of charge storage and electrode interactions, as well as battery design and performance.

Enhanced High-Temperature Electrical Resistivity of Aluminum Nitride Obtained by Engineering a Schottky Barrier at Grain Boundaries

An enhanced high-temperature electrical resistivity of AlN at high voltage was obtained by using MgO doping to modulate the Schottky barrier. Doped MgO was precipitated in an ∼100-nm-thick layer near grain boundaries, which reduced not only anionic carriers, but also the carrier mobility, due to the formation of defects (Mg′Al, O·N). According to an impedance analysis, the activation energy and the resistivity due to grain boundaries were increased by MgO doping, suggesting an elevated Schottky barrier. As a result, a remarkable high-voltage electrical resistivity, which is greater than 1010 Ω·cm at 550 °C/100 V, can be achieved, which is valuable for electrostatic chucking devices.

Mobility of Charge Carriers in a Single Crystal and Nanoceramic of the Superionic Pb1 – xSnxF2 Conductor (x = 0.2)

A crystallophysical model of ion transfer in the superionic Pb1 – xSnxF2 conductor with a fluorite (CaF2) structure is proposed. The concentration dependence of the ionic conductivity of Pb1 – xSnxF2 single crystals and poly- and nanocrystals is analyzed. The single-crystal form of the superionic conductor is characterized by the highest conductivity. The mobility and concentration of anionic charge carriers in a single crystal and ceramics of Pb1 – xSnxF2 (x = 0.2) is calculated on the basis of structural and electrophysical data. The mobility of carriers μmob = 2.5 × 10–6 cm2/s V (at 293 K) in a single crystal is seven times higher than in nanoceramic. The concentration of carriers nmob = 1.7 × 1021 and 3.6 × 1021 cm3 (4.5 and 9.5% of the total number of anions) for a single crystal and nanoceramic, respectively. The comparison of isostructural Pb0.8Sn0.2F2, Pb0.67Cd0.33F2, and Pb0.9Sc0.1F2.1 single crystals shows that anionic carriers have a maximum mobility in the β-PbF2 and SnF2 based solid solution.

Commencing mild Ag–Zn batteries with long-term stability and ultra-flat voltage platform

Alkaline Silver (Ag)-Znic (Zn) batteries have been suffering from poor cyclic stability for over one century but the comprehensively improving protocol is still in vacancy with big challenge. Here, we commence a mild Ag–Zn battery to simultaneously solve the cathode dissolving issue and anode dendrite issue. The battery proceeds through anionic halides as charging carriers for cathode reactions, endowing two phase transition process with ultra-flat discharging voltage plateau. The battery delivered unprecedently elongated cyclic lifetime to 1300 cycles in contrast to conventional alkaline Ag–Zn battery (<100 cycles). This work not only solved the long-term cyclic issue of Ag–Zn battery but also would act as a model system to introduce mild electrolyte and anionic charging carriers into other aqueous battery systems for performance improvement.

Low-density solvent-based dispersive liquid-liquid microextraction followed by HPLC-ICP-MS for speciation analysis of phenylarsenics in lake water

ABSTRACTA simple and fast method of low-density solvent based dispersive liquid-liquid microextraction (LDS-DLLME) followed by high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) has been developed for the speciation analysis of organoarsenic and inorganic arsenic in water samples. The low-density solvent (octanol) was given as the organic phase and injected into the aqueous sample (donor phase) with methanol as the disperser. With As (V), As (III), p-APAA, 4-HPAA, ROX and PAA as target species, factors of LDS-DLLME including pH value, anionic carriers, elution conditions and extractant, were studied in detail. Besides, volumes of solvents were further optimised by response surface methodology. Under the optimal conditions, the limits of detection for four phenylarsenics and arsenate were in the range of 0.001–0.039 μg L−1. The relative standard deviations (RSDs) were 3.6–9.4% and the enrichment factors varied from 6.2 to 70.8. The proposed method of LDS-DLLME-HPLC-ICP-MS was satisfactorily applied to the determination of six arsenic compounds in water samples with recoveries of 81.8–111.7% for the spiked lake water samples.

Подвижность носителей заряда в монокристалле и нанокерамике суперионного проводника Pb-=SUB=-1-x-=/SUB=-Sn-=SUB=-x-=/SUB=-F-=SUB=-2-=/SUB=- (x=0.2)

AbstractA crystallophysical model of ion transfer in the superionic Pb_1 – _ x Sn_ x F_2 conductor with a fluorite (CaF_2) structure is proposed. The concentration dependence of the ionic conductivity of Pb_1 – _ x Sn_ x F_2 single crystals and poly- and nanocrystals is analyzed. The single-crystal form of the superionic conductor is characterized by the highest conductivity. The mobility and concentration of anionic charge carriers in a single crystal and ceramics of Pb_1 – _ x Sn_ x F_2 ( x = 0.2) is calculated on the basis of structural and electrophysical data. The mobility of carriers μ_mob = 2.5 × 10^–6 cm^2/s V (at 293 K) in a single crystal is seven times higher than in nanoceramic. The concentration of carriers n _mob = 1.7 × 10^21 and 3.6 × 10^21 cm^3 (4.5 and 9.5% of the total number of anions) for a single crystal and nanoceramic, respectively. The comparison of isostructural Pb_0.8Sn_0.2F_2, Pb_0.67Cd_0.33F_2, and Pb_0.9Sc_0.1F_2.1 single crystals shows that anionic carriers have a maximum mobility in the β-PbF_2 and SnF_2 based solid solution.

DNA Nanostructure-Programmed Like-Charge Attraction at the Cell-Membrane Interface.

Cell entry of anionic nano-objects has been observed in various types of viruses and self-assembled DNA nanostructures. Nevertheless, the physical mechanism underlying the internalization of these anionic particles across the negatively charged cell membrane remains poorly understood. Here, we report the use of virus-mimicking designer DNA nanostructures with near-atomic resolution to program “like-charge attraction” at the interface of cytoplasmic membranes. Single-particle tracking shows that cellular internalization of tetrahedral DNA nanostructures (TDNs) depends primarily on the lipid-raft-mediated pathway, where caveolin plays a key role in providing the short-range attraction at the membrane interface. Both simulation and experimental data establish that TDNs approach the membrane primarily with their corners to minimize electrostatic repulsion, and that they induce uneven charge redistribution in the membrane under the short-distance confinement by caveolin. We expect that the nanoscale like-charge attraction mechanism provides new clues for viral entry and general rules for rational design of anionic carriers for therapeutics.

Sodium Transporters Are Involved in Lithium Influx in Brain Endothelial Cells.

Variability in drug response to lithium (Li+) is poorly understood and significant, as only 40% of patients with bipolar disorder highly respond to Li+. Li+ can be transported by sodium (Na+) transporters in kidney tubules or red blood cells, but its transport has not been investigated at the blood-brain barrier (BBB). Inhibition and/or transcriptomic strategies for Na+ transporters such as NHE (SLC9), NBC (SLC4), and NKCC (SLC12) were used to assess their role on Li+ transport in human brain endothelial cells. Na+-free buffer was also used to examine Na+/Li+ countertransport (NLCT) activity. The BBB permeability of Li+ evaluated in the rat was 2% that of diazepam, a high passive diffusion lipophilic compound. Gene expression of several Na+ transporters was determined in hCMEC/D3 cells, human hematopoietic stem-cell-derived BBB models (HBLEC), and human primary brain microvascular endothelial cells (hPBMECs) and showed the following rank order with close expression profile: NHE1 > NKCC1 > NHE5 > NBCn1, while NHE2-4, NBCn2, and NBCe1-2 were barely detected. Li+ influx in hCMEC/D3 cells was increased in Na+-free buffer by 3.3-fold, while depletion of chloride or bicarbonate had no effect. DMA (NHE inhibitor), DIDS (anionic carriers inhibitor), and bumetanide (NKCC inhibitor) decreased Li+ uptake significantly in hCMEC/D3 by 52, 51, and 47%, respectively, while S0859 (NBC inhibitor) increased Li+ influx 2.3-fold. Zoniporide (NHE1 inhibitor) and siRNA against NHE1 had no effect on Li+ influx in hCMEC/D3 cells. Our study shows that NHE1 and/or NHE5, NBCn1, and NKCC1 may play a significant role in the transport of Li+ through the plasma membrane of brain endothelial cells.

A study on the potential of using plant proteins as electrolytes in a biochemical cell

We demonstrate that proteins extracted from nonedible oil meals can be used as inexpensive, renewable, and biodegradable electrolytes in biochemical cells. Electrolytes are the critical components of cells and generally made using metals, ionic, or salt solutions. These electrolytes are either expensive, harmful to the environment when disposed and/or provide poor performance. Proteins behave as anionic or cationic charge carriers depending on the environment there are in. Recent increase in the production of biodiesel from oil seeds has led to the abundant availability of protein containing oil meals. These oil meals inherently and inevitably contain the proteins and are available in large quantities at low cost. In this report, we have extracted proteins from three different oil meals. Proteins obtained were used as electrolytes with different electrodes and operating conditions. A voltage of up to 300 mV was generated using copper electrodes as both anode and cathode. Protein concentration of 10% was found to be optimum and increasing time substantially reduces the voltage for all the electrodes. Although higher voltage could be generated when dissimilar electrodes were used, the contribution from the proteins to the charge generated was minimal. Maximum current generated was about 9 mA when a 10 ohm resistor was connected as load. Utilizing proteins from nonedible oil meals will provide inexpensive and environmentally friendly electrolytes for biochemical cells. This is the first time that proteins have been used as electrolytes for biochemical cells. More importantly, we have used the byproduct generated during production of biodiesel as source for the proteins. This makes the proteins inexpensive, biodegradable and widely available. At the same time, high value addition is possible to the byproduct which will lead to lowering the cost of the biodiesel. © 2017 American Institute of Chemical Engineers Environ Prog, 37: 961–967, 2018

Single stranded siRNA complexation through non-electrostatic interactions.

As double stranded, single stranded siRNA (ss-siRNA) has demonstrated gene silencing activity but still requires efficient carriers to reach its cytoplasmic target. To better understand the fundamental aspect driving the complexation of ss-siRNA with nanocarriers, the interactions between surfaces of various compositions across a ss-siRNA solution were investigated using the Surface Forces Apparatus. The results show that ss-siRNA can adsorb onto hydrophilic (positively and negatively charged) as well as on hydrophobic substrates suggesting that the complexation can occur through hydrophobic interactions and hydrogen bonding in addition to electrostatic interactions. Moreover, the binding strength and the conformation of ss-siRNA depend on the nature of the interactions between the ss-siRNA and the surfaces. The binding of ss-siRNA with nanocarriers, such as micelles or liposomes through non-electrostatic interactions was also evidenced by a SYBR® Gold cyanine dye. We evidenced the presence of interactions between the dye and oligonucleotides already complexed to non-cationic nanovectors biasing the quantification of the encapsulation. These results suggest that non-electrostatic interactions could be exploited to complement electrostatic interactions in the design of nanocarriers. In particular, the different highlighted interactions can be used to complex ss-siRNA with uncharged or anionic carriers which are related to lower toxicity compared to cationic carriers.

On the mechanism of electrical conductivity in Ce1/3NbO3

Using electrical conductivity measurements, we found the existence of different activation energy values for the electric transport in Ce1/3NbO3: 0.78eV for T>800°C and 0.39eV for T<800°C. Atomistic simulations have shown that the energy required to move the Ce3+ ions is around 8eV, which is one order of magnitude higher of what is experimentally found. Additionally, electrical measurements at different partial pressures of oxygen show that the material has oxygen-ion conductivity, but the activation energy of 0.39eV suggests other possible mechanisms of electrical conductivity. One of these possibilities is electronic transport, where the activation energy could be due to the band gap. To determine whether electronic conductivity is contributing in the low temperature regime, we performed ab-initio DFT electronic calculations to evaluate the gap, using the modified Becke–Johnson potential. Due to a Ce:4f level found in the gap, which obstructed the convergence of the calculation, we used the LDA+U approach on the Ce atoms, this moves the 4f levels out of the gap. We used the values U=1, 2 and 3eV, then extrapolated back to U=0 to find the location of the Ce:4f state in the gap. The computed value of the activation energy for electronic conductivity is higher than the experimental one, and resembles more the optical gap value found in Ce1/3NbO3. Based on this result, it can be inferred that the electrical conductivity in Ce1/3NbO3 proceeds via anionic charge carriers in the entire temperature studied range.

ChemInform Abstract: A Review on Recent Developments of Anion Exchange Membranes for Fuel Cells and Redox Flow Batteries

AbstractReview: 216 refs.