1,4-Diaminoanthraquinones (DAAQs) are a promising class of redox-active molecules for use in nonaqueous redox flow batteries (RFBs) because they can have up to five electrochemically accessible and reversible oxidation states. However, most of the commercially available DAAQs have a low solubility in the polar organic solvents that are typically used in RFBs, in particular when supporting electrolyte salts are present. This significantly limits the energy densities that can be achieved. We have functionalized the amino groups in the DAAQ structure with three types of chains, namely alkyl chains, cationic alkyl chains and oligoethylene glycol ether chains, and measured the solubility of these derivatives in various organic solvents by quantitative UV-Vis absorption spectroscopy. The DAAQ derivatives with higher polarity exhibit a significantly higher solubility in commonly used organic electrolytes in comparison to apolar derivatives. Cyclic voltammetry was used to assess the viability of the DAAQs as redox-active species for RFBs. Although the cationic DAAQ derivatives have an enhanced solubility in the electrolytes, the cathodic redox reactions have a poor reversibility, most likely due to an internal decomposition reaction of their reduced forms. The oligoethylene-glycol-ether-functionalized DAAQs are the most promising compounds for use in organic RFB electrolytes because they have the optimal combination of high solubility and a high reversibility of the redox couples.

Various overoxidized poly(1H-pyrrole) (PPy), poly(N-methylpyrrole) (PMePy) or poly(3,4-ethylenedioxythiophene) (PEDOT) membranes incorporated into an acrylate-based solid polymer electrolyte matrix (SPE) were directly electrosynthesized by a two-step in situ procedure. The aim was to extend and improve fundamental properties of pure SPE materials. The polymer matrix is based on the cross-linking of glycerol propoxylate (1PO/OH) triacrylate (GPTA) with poly(ethylene glycol) diacrylate (PEGDA) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as a conducting salt. A self-standing and flexible polymer electrolyte film is formed during the UV-induced photopolymerization of the acrylate precursors, followed by an electrochemical polymerization of the conducting polymers to form a 3D-IPN. The electrical conductivity of the conducting polymer is destroyed by electrochemical overoxidation in order to convert the conducting polymer into an ion-exchange membrane by introduction of electron-rich groups onto polymer units. The resulting polymer films were characterized by scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectroscopy, differential scanning calorimetry, thermal analysis and infrared spectroscopy. The results of this study show that the combination of a polyacrylate-matrix with ion selective properties of overoxidized CPs leads to new 3D materials with higher ionic conductivity than SPEs and separator or selective ion-exchange membrane properties with good stability by facile fabrication.

This work figures out the material balance of the reactions occurring in the O2 electrode of a Li-O2 cell, where a Ketjenblack-based porous carbon electrode comes into contact with a tetraethylene glycol dimethyl ether (TEGDME)-based electrolyte under more practical conditions of less electrolyte amount and high areal capacity. The ratio of electrolyte weight to cell capacity (E/C, g A h-1) is a good parameter to correlate with cycle life. Only 5 cycles were obtained at an areal capacity of 4 mA h cm-2 (E/C = 10) and a discharge/charge current density of 0.4 mA cm-2, which corresponds to the energy density of 170 W h kg-1 at a complete cell level. When the areal capacity was decreased to half (E/C = 20) by setting a current density at 0.2 mA cm-2, the cycle life was extended to 18 cycles. However, the total electric charge consumed for parasitic reactions was 35 and 59% at the first and the third cycle, respectively. This surprisingly large amount of parasitic reactions was suppressed by half using redox mediators at 0.4 mA cm-2 while keeping a similar cycle life. Based on by-product distribution, we will propose possible mechanisms of TEGDME decomposition and report a water breathing behavior, where H2O is produced during charge and consumed during discharge.

Solid polymer electrolytes (SPEs) for Li-metal polymer batteries are prepared, in which poly(ethylene oxide) (PEO), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), and copper-oxide fillers are formulated. Their structural and electrochemical properties are analyzed when the morphology of the copper-oxide fillers has been modulated to spherical or dendritic structure. The ionic conductivity obtained by electrochemical impedance spectroscopy (EIS) has been increased to 1.007 × 10-4 S cm-1 at 30 °C and 1.368 × 10-3 S cm-1 at 60 °C, as the 5 wt% dendritic fillers have been added to the SPEs. This ionic conductivity value is 1.3 times higher than that of 5 wt% spherical filler-contained SPEs. The analyses of differential scanning calorimetry (DSC) and X-ray diffraction (XRD) indicate that the increase of ionic conductivity is due to the remarkable decrease of crystallinity upon the addition of copper-oxide filler into PEO matrix of SPEs. The fabricated SPEs with the dendritic copper-oxide fillers present a total ionic transference number of 0.99 and a lithium-ion transference number of 0.38. More importantly, it presents a stable potential window of 2.0-4.8 V at 25 °C and high thermal stability up to 300 °C. The specific discharge capacity of the prepared cell with the dendritic filler-contained SPEs is measured to be 51 mA h g-1 and 125 mA h g-1 under 0.1 current-rate (C-rate) at 25 °C and 60 °C, respectively. In this study, the ionic conductivity and the electrochemical performance of the PEO-based polymer electrolyte have been evaluated when morphologically different copper-oxide fillers have been incorporated into the PEO matrix. We have also confirmed the safety and the flexibility of the prepared solid polymer electrolytes when they are used in flexible lithium-metal polymer batteries (LMPBs).

The lithium ion battery (LIB) is the most popular choice for powering consumer electronics, grid storage and electric vehicles. Decomposition reactions in LIBs, leading to so-called aging, are the main reason for loss of capacity and power and will affect LIB safety. Organo(fluoro)phosphates (O(F)Ps) as decomposition products of LIB electrolytes have been identified in several studies in the literature but quantitative data of O(F)Ps in LIBs are only scarcely available. In terms of toxicity, this substance class is highly relevant as it shows structural similarities to chemical warfare agents. Thus, approaches that can deliver quantitative data are in need. In this study, acidic O(F)Ps were quantified with an inductively coupled plasma-sector field-mass spectrometer (ICP-SF-MS) after separation of species with hydrophilic interaction liquid chromatography (HILIC). The formation of OFPs exceeds the amount of non-fluorine containing OPs by a factor of up to 15. A total of 16 different O(F)P compounds could successfully be quantified. Organic mass spectrometry was used for the assignment of quantitative data.

Thin films of Co and Ni electroplated onto a copper electrode from acidic sulfate and Watts baths, respectively, were investigated. The use of an ionic liquid additive in the electrolyte is widespread for producing thin films by electrodeposition. In the present work, the influence of a new ionic liquid, namely, 1-methyl-3-((2-oxo-2-(2,4,5-trifluorophenyl)amino)ethyl)-1H-imidazol-3-ium iodide (Im-IL), in the electrodeposition of two metals was investigated using cathodic polarization (CP), cyclic voltammetry (CV), and anodic linear stripping voltammetry (ALSV) measurements and cathodic current efficiency (CCE%). The surface morphology of the Co- and Ni-coated samples was examined using Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and atomic force microscopy (AFM). The corrosion protection of the Co and Ni samples in a marine environment (3.5% NaCl solution) was studied by the potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The results show that the addition of Im-IL inhibits Co2+ and Ni2+ deposition, which leads to more fine-grained deposits, especially at low Im-IL concentrations. The inhibition of Co2+ and Ni2+ reduction in the presence of Im-IL ions occurs via adsorption, which obeys the Langmuir adsorption isotherm. The CCE% is higher in the presence of Im-IL. SEM images show smoother deposits of Co and Ni in 1 × 10-5 M and 1 × 10-4 M Im-IL solution respectively. The results prove that Im-IL acts as an efficient additive for electroplating soft Co and Ni films.

Liquid-phase synthesis is a useful technique for preparing argyrodite sulfide-based solid electrolytes, and the synthesis conditions such as heat treatment strongly affect the conductivity. Because the understanding of structural changes reveals crucial information about their properties, it is necessary to evaluate this change during heat treatment to determine the factors that affect the conductivity. In this study, X-ray diffraction measurements and transmission electron microscope observations reveal the effects of heat treatment on the crystallinities and ionic conductivities in the synthesis process of argyrodite electrolytes with tetrahydrofuran and ethanol. The amorphous material is in the main phase when heated at low temperatures below 200 °C and exhibits relatively low conductivities of ca. 2 × 10-4 S cm-1 despite precipitation of the argyrodite crystals. As the heat treatment temperature increases, the ratio of argyrodite crystals increases, involving nucleation and grain growth, leading to high conductivities of over 10-3 S cm-1. It is critical to control the ratio of the amorphous and crystal phases to achieve high conductivities in the synthesis of argyrodite electrolytes via liquid-phase processing.

Herein we demonstrate how peat, abundant and cheap biomass, can be successfully used as a precursor to synthesize peat-derived hard carbons (PDCs), applicable as electrode materials for sodium-ion batteries (SIB). The PDCs were obtained by pre-pyrolysing peat at 300-800 °C, removing impurities with base-acid solution treatment and thereafter post-pyrolysing the materials at temperatures (T) from 1000 to 1500 °C. By modification of pre- and post-pyrolysis temperatures we obtained hard carbons with low surface areas, optimal carbonization degree and high electrochemical Na+ storage capacity in SIB half-cells. The best results were obtained when pre-pyrolysing peat at 450 °C, washing out the impurities with KOH and HCl solutions and then post-pyrolysing the obtained carbon-rich material at 1400 °C. All hard carbons were electrochemically characterized in half-cells (vs. Na/Na+) and capacities as high as 350 mA h g-1 at 1.5 V and 250 mA h g-1 in the plateau region (E < 0.2 V) were achieved at charging current density of 25 mA g-1 with an initial coulombic efficiency of 80%.

The physicochemical properties of three new magnesium-containing solvate ionic liquids are reported. The solvation structures were analysed by Raman spectroscopy, revealing a solvent separated ion pair structure at room temperature. The reversible electrodeposition and stripping of magnesium from mixtures of these solvate ionic liquids and tetra-n-butylammonium chloride is described. The electrolytes are significantly less volatile than similar dilute electrolytes, even at elevated temperatures and the deposition current densities exceed 1 A dm-2 at 80 °C. The influence of the chloride concentration on magnesium deposition was studied with cyclic voltammetry and chronopotentiometry. It was found that the stripping of magnesium is governed by two competing reactions, and the addition of tetrabutylammonium chloride to the solvate ionic liquids was necessary to prevent passivation and efficiently strip the deposited magnesium.

A processing solvent-free manufacturing process for cross-linked ternary solid polymer electrolytes (TSPEs) is presented. Ternary electrolytes (PEODA, Pyr14TFSI, LiTFSI) with high ionic conductivities of >1 mS cm-1 are obtained. It is shown that an increased LiTFSI content in the formulation (10 wt% to 30 wt%) decreases the risk of short-circuits by HSAL significantly. The practical areal capacity increases by more than a factor of 20 from 0.42 mA h cm-2 to 8.80 mA h cm-2 before a short-circuit occurs. With increasing Pyr14TFSI content, the temperature dependency of the ionic conductivity changes from Vogel-Fulcher-Tammann to Arrhenius behavior, leading to activation energies for the ion conduction of 0.23 eV. In addition, high Coulombic efficiencies of 93% in Cu‖Li cells and limiting current densities of 0.46 mA cm-2 in Li‖Li cells were obtained. Due to a temperature stability of >300 °C the electrolyte guarantees high safety in a broad window of conditions. In LFP‖Li cells, a high discharge capacity of 150 mA h g-1 after 100 cycles at 60 °C was achieved.

A novel positively charged composite nanofiltration (NF) membrane with tunable active layer structure was successfully developed via interfacial polymerization on a polysulfone (PSF) ultrafiltration (UF) membrane surface, using polyethyleneimine (PEI) as the monomer of the aqueous phase, and a mixture of isophthaloyl dichloride (IPC) and tri-mesoyl chloride (TMC) as the monomer of the organic phase. Interestingly, a synergetic effect of the mass ratio of IPC and TMC was observed on the pore size and the structure of the active layer of the resultant polyamide (PA)/polysulfone (PSF) composite NF membrane. The rejection (R) to the inorganic electrolytes increased with the mass ratio of IPC to TMC, while the permeate flux (F) escalated up to a 1 : 1 mixing ratio of IPC to TMC and dropped at higher mixing ratios. The rejection to different inorganic electrolytes decreased in the order of ZnCl2, MgCl2, CaCl2, CuCl2, MgSO4, NaCl, and Na2SO4. At ambient temperature and 0.4 MPa, the optimized membrane demonstrated R and F to 1 g L-1 MgCl2 aqueous solution as 98.1% and 27.6 L m-2 h-1, respectively. Its rejection to various dyes reduced significantly in the order of cationic red X-GTL (100%), rhodamine B (94.2%), cationic gold yellow X-GL (93.5%), and brilliant blue KN-R (43.9%), in agreement with the decrease in the molecular weight (M w) and the overall charges of the dye.

Doping modification is regarded as a simple and effective method for increasing the ionic conductivity and air stability of solid state electrolytes. In this work, a series of (100-x)(0.75Li2S·0.25P2S5)·xP2O5 (mol%) (x = 0, 1, 2, 3 and 4) glass-ceramic electrolytes were synthesized by a two-step ball milling technique. Various characterization techniques (including powder X-ray diffraction, Raman and solid-state nuclear magnetic resonance) have proved that the addition of P2O5 can stimulate 75Li2S·25P2S5 system to generate the high ionic conductivity phase Li7P3S11. Through the doping optimization strategy, 98(0.75Li2S·0.25P2S5)·2P2O5 glass-ceramic (2PO) not only had a 3.6 times higher ionic conductivity than the undoped sample but also had higher air stability. Its ionic conductivity remained in the same order of magnitude after 10 minutes in the air. We further investigated the reasons why 2PO has a relatively high air stability using powder X-ray diffraction and scanning electron microscopy in terms of crystal structure degradation and morphology changes. In comparison to the undoped sample, the high ionic conductivity phases (β-Li3PS4 and Li7P3S11) of 2PO were better preserved, and less impurity and unknown peaks were generated over a short period of exposure time. In addition, the morphology of 2PO only changed slightly after 10 minutes of exposure. Despite the fact that the particles aggregated significantly after several days of exposure, 2PO tended to form a protective layer composed of S8, which might allow some particles to be shielded from attack by moisture, slowing down the decay of material properties.

To enhance the electrochemical properties of silicon anodes in lithium-ion batteries, dimethylacrylamide (DMAA) was selected as a novel electrolyte additive. The addition of 2.5 wt% DMAA to 1.0 M LiPF6/EC : DMC : DEC : FEC (3 : 3 : 3 : 1 weight ratio) electrolyte significantly enhanced the electrochemical properties of the silicon anode including the first coulombic efficiency, rate performance and cycle performance. The solid electrolyte interphase (SEI) layers developed on the silicon anode in different electrolytes were investigated by a combination of electrochemical and spectroscopic studies. The improved electrochemical performances of the Si anode were ascribed to the effective passivation of DMAA on the silicon anode. The addition of DMAA helped develop a uniform SEI layer, which prevented side reactions at the interface of silicon and electrolyte.

Development of highly efficient oxygen evolution reaction (OER) electrocatalysts is a critical challenge in the cost-effective generation of clean fuels. Here, a metal-free tyramine functionalized graphene oxide (T-GO) electrocatalyst is proposed to use in alkaline electrolytes for enhanced OER. Moreover, the T-GO and GO nanomaterials are well characterized by SEM, XRD, FTIR, XPS and Raman spectroscopy. T-GO exhibits an electrocatalytic OER with a current density of 2 mA cm-2 at a low onset potential of ∼1.39 V and a small Tafel slope of about 69 mV dec-1 and GO exhibits an onset potential of 1.51 V and Tafel slope of about 92 mV dec-1. Additionally, the current stability and RRDE based diffusion controlled response of the T-GO electrocatalyst are outstanding compared to GO. This study establishes metal free T-GO as an efficient electrocatalyst for the OER and used for cathodic production of hydrogen as a counter reaction in the field of water splitting.

Wearable electrochemical sensors have attracted tremendous attention in recent years. Here, a three-dimensional paper-based microfluidic electrochemical integrated device (3D-PMED) was demonstrated for real-time monitoring of sweat metabolites. The 3D-PMED was fabricated by wax screen-printing patterns on cellulose paper and then folding the pre-patterned paper four times to form five stacked layers: the sweat collector, vertical channel, transverse channel, electrode layer and sweat evaporator. A sweat monitoring device was realized by integrating a screen-printed glucose sensor on polyethylene terephthalate (PET) substrate with the fabricated 3D-PMED. The sweat flow process in 3D-PMED was modelled with red ink to demonstrate the capability of collecting, analyzing and evaporating sweat, due to the capillary action of filter paper and hydrophobicity of wax. The glucose sensor was designed with a high sensitivity (35.7 μA mM-1 cm-2) and low detection limit (5 μM), considering the low concentration of glucose in sweat. An on-body experiment was carried out to validate the practicability of the three-dimensional sweat monitoring device. Such a 3D-PMED can be readily expanded for the simultaneous monitoring of alternative sweat electrolytes and metabolites.

Polypyrrole/expanded graphite (PPy/EG) nanohybrids, with a hierarchical structure of a three dimensional EG framework with a thick PPy coating layer, have been synthesized via a vacuum-assisted intercalation in situ oxidation polymerization method. In the synthesis, pyrrole monomers were intercalated into the irregular pores of EG with the assistance of a vacuum pump. Subsequently, the intercalated pyrrole monomers assembled on both sides of the EG nanosheets and formed PPy by an in situ polymerization method. As electrode materials, the typical PPy/EG10 sample with an EG content of 10% had a high specific capacitance of 454.3 F g-1 and 442.7 F g-1 (1.0 A g-1), and specific capacitance retention rate of 75.9% and 73.3% (15.0 A g-1) in 1 M H2SO4 and 1 M KCl electrolytes, respectively. The two-electrode symmetric supercapacitor showed a high energy density of 47.5 W h kg-1 at a power density of 1 kW kg-1, and could retain superb stability after 2000 cycles. The unique self-supporting structure feature and homogeneous PPy nanosphere coating combined the contributions of electrochemical double layer capacitance and pseudo-capacitance, which made the nanohybrids an excellent electrode material for high performance energy storage devices.

Artemisia vulgaris seeds extrude hydrogel (AVH), which shows extraordinary swelling in water, at pH 6.8, and 7.4, which follows second-order kinetics. AVH exhibits reversible swelling/deswelling in ethanol and normal saline as well at pH 7.4 and pH 1.2. Therefore, AVH shows stimuli-responsiveness in different physiological conditions, solvents, and electrolytes. The superporous nature of AVH in swollen/freeze-dried sculpture is exposed in their SEM micrographs. AVH-based aceclofenac tablet formulations offer sustained-release under simulated conditions of the gastrointestinal tract (GIT) in terms of pH and transit time. Pharmacokinetic studies also show the delay and prolonged plasma concentration with t max of 8 h, therefore, such formulations can be used to enhance the bioavailability of aceclofenac. The swelling behavior of the AVH tablet is also assessed using MRI. The in vivo fate of the AVH tablet is monitored by X-ray during the transit through the GIT. Acute toxicity studies of AVH indicate the absence of any toxicity which reveals the safety profile of AVH. Therefore, AVH can be used for oral, topical and ophthalmic drug delivery systems. These results establish the potential of AVH as a stimuli sensitive, pH-dependent, and sustained-release biomaterial for targeted drug delivery.

Nanopore probing of molecular level transport of proteins is strongly influenced by electrolyte type, concentration, and solution pH. As a result, electrolyte chemistry and applied voltage are critical for protein transport and impact, for example, capture rate (C R), transport mechanism (i.e., electrophoresis, electroosmosis or diffusion), and 3D conformation (e.g., chaotropic vs. kosmotropic effects). In this study, we explored these using 0.5-4 M LiCl and KCl electrolytes with holo-human serum transferrin (hSTf) protein as the model protein in both low (±50 mV) and high (±400 mV) electric field regimes. Unlike in KCl, where events were purely electrophoretic, the transport in LiCl transitioned from electrophoretic to electroosmotic with decreasing salt concentration while intermediate concentrations (i.e., 2 M and 2.5 M) were influenced by diffusion. Segregating diffusion-limited capture rate (R diff) into electrophoretic (R diff,EP) and electroosmotic (R diff,EO) components provided an approach to calculate the zeta-potential of hSTf (ζ hSTf) with the aid of C R and zeta potential of the nanopore surface (ζ pore) with (ζ pore-ζ hSTf) governing the transport mechanism. Scrutinization of the conventional excluded volume model revealed its shortcomings in capturing surface contributions and a new model was then developed to fit the translocation characteristics of proteins.

The application of triphenylene-based discotic liquid crystal derivatives as physical gelators is investigated. In particular, we focus on 2,3,6,7,10,11-hexakis-pentyloxytriphenylene (HAT5) and the longer alkyl chain homologue (HAT6). The driving mechanisms behind and parameter space of non-covalent physical gel formation is studied. A Hansen solubility parameter (HSP) approach is used to predict physical gelation of these disc-like liquid crystalline molecules in a variety of common organic and inorganic solvents important to electrochemical devices. Our results show that HSP analysis is very useful for the prediction of gel formation. The results are transferrable and can form the basis for future investigations into liquid crystalline physical gels. Furthermore, we use acetonitrile as a solvent and apply the gels as electrolytes in dye sensitized solar cells. It is observed that using a binary mixture of gelators results in average photovoltaic power conversion efficiencies as high as 7.21%, compared to a 5.9% reference electrolyte. This is attributed to a reduction in electron recombination at the n-type interface and provides further insight about hybrid gelators. Coupled with an increase in device stability, the results are promising for gel-based dye sensitized solar cells as well as potentially other electrolytic devices such as batteries and supercapacitors.

N-doped porous carbon nanospheres were fabricated directly by pyrolyzing chitin nanogels, which were facilely prepared by mechanical agitation induced sol-gel transition of chitin solution in NaOH/urea solvent. The resulting carbon nanospheres displayed ordered micropores (centered at ∼0.6 nm) and high BET surface area of up to 1363 m2 g-1, which is substantially larger than that of the carbons from raw chitin (600 m2 g-1). In addition, the carbon nanospheres retained a nitrogen content of 3.2% and excellent conductivity. Consequently, supercapacitor electrodes prepared from the carbon nanospheres pyrolyzed at 800 °C showed a specific capacitance as high as 192 F g-1 at a current density of 0.5 A g-1 and impressive rate capability (81% retention at 10 A g-1). When assembled in a symmetrical two-electrode cell, N-doped porous carbon nanospheres demonstrated excellent cycling stability both in aqueous and organic electrolytes (95% retention after 10 000 cycles at 10 A g-1), together with outstanding energy density of 5.1 W h kg-1 at the power density of 2364.9 W kg-1. This work introduces a novel and efficient method to prepared N-doped porous carbon nanospheres directly from chitin and demonstrates the great potential of utilization of abundant polymers from nature in power storage.