Electrodeposition of Rare Earth Metals and Their Alloys in Organic Electrolytes

The electrodeposition of rare earth metals and their alloys in organic electrolytes are reviewed. The solvents, electrolytes and operetating conditions are discussed. It is concluded that exploring the rare earth salt, which can be highly soluble in organic solvents and easily dehydrated, is the key to the pracitical utilization of electrodeposition of rare earth metals and their alloys in organic electrolytes.

Rational design of viologen redox additives for high-performance supercapacitors with organic electrolytes

Introducing redox species into the electrolytes of traditional electric double layer capacitors(EDLCs)is an efficient strategy to enhance their energy density owing to Faradic reactions.However,few studies have elucidated the effect of the molecular structures of organic redox species on the performance of relative supercapacitors,which is important in the development of redox additives for super-capacitors.In this context,we synthesized several viologens and used them as new organic redox additives for super-capacitors with organic electrolytes.The detailed experimental analysis and theoretical calculation results show that the electrochemical performance of viologens relies heavily on their side chains and conjugated cores.Specifically,the side chains of the viologens affect their electronic structures and are consistent with behaviours between the molecules and the electrode pores due to the size effect,thus influencing their specific capacities.In addition,a larger conjugated aromatic core endows viologens with a smaller band gap and a higher degree of electron delocalization,resulting in better rate performance and cycling stability.Consequently,aπ-conjugated viologen derivative is selected as a favourable additive and enables an EDLC-type supercapacitor to exhibit a high energy density(34.0 W h kg^−1 at 856 W kg^−1)and good cycling performance.

Effect of surface area and heteroatom of porous carbon materials on electrochemical capacitance in aqueous and organic electrolytes

A series of porous carbon materials with wide range of specific surface areas and different heteroatom contents had been prepared using polyaniline as carbon precursor and KOH as an activating agent. Effect of surface area and heteroatom of porous carbon materials on specific capacitance was investigated thoroughly in two typical aqueous KOH and organic 1-butyl-3- methylimidazolium tetrafluoroborate/acetonitirle electrolytes. The different trends of capacitance performance were observed in these two electrolytes. Electrochemical analyses suggested that the presence of faradaic interactions on heteroatom-enriched carbon materials in organic environment is less significant than that observed in aqueous electrolytes. Thus, in aqueous electrolyte, a balance between surface area and heteroatom content of activated porous carbon would be found to develop a supercapacitor with high energy density. In organic electrolyte, the capacitance performance of porous carbon is strongly dependent on the surface area. The results may be useful for the design of porous carbon-based supercapacitor with the desired capacitive performance in aqueous and organic electrolytes.

Solubility study and selective purification of HMX explosive in organic electrolyte solution of zinc acetate/diethylene glycol

In this study, an organic electrolyte solution based on zinc acetate/diethylene glycol(ZA/DEG) is introduced for the selective purification of cyclotetramethylene tetranitramine(HMX) high explosive from its identical homologue cyclotrimethylene trinitramine(RDX). The dielectric constant of various organic solutions were investigated through Electrochemical Impedance Spectroscopy(EIS) in the range of 1.0 Hz—30 MHz. and some quantum-chemical descriptors of RDX and HMX dissolutions in the ZA cosolvent were analyzed using Density Functional Theory(DFT). The results show dielectric constant and solubility of RDX is higher than that of HMX, and by increasing of ZA concentration in DEG solvent, the values of dielectric constants were enhanced. Furthermore, the presence of ZA cosolvent on the solubility of two explosives was statistically investigated by Central Composite Design(CCD) of experiment, and some solubility parameters including activity coefficient, dissolving enthalpy, and mixing enthalpies were determined. The experimental results indicate that the weight ratio of RDX to HMX solubility in the proposed organic electrolyte changes up to 30 times, which provides a selective and sequential separation method to separate two materials with similar chemical properties with a separation efficiency>98% and HMX purity> 99.8%. The X-Ray Diffraction(XRD) analysis, High-Performance Liquid Chromatography(HPLC), Laser-Induced Breakdown Spectroscopy(LIBS), and Fourier Transform Infrared Spectroscopy(FT-IR) approves the acceptable quality of the separated materials. The proposed method makes the efficient and safe purification of high-quality HMX for application in oil and gas well perforating gun charges, using a nonvolatile and inflammable organic electrolyte.

The safety aspect of sodium ion batteries for practical applications

Sodium-ion batteries(SIBs)with advantages of abundant resource and low cost have emerged as promising candidates for the next-generation energy storage systems.However,safety issues existing in electrolytes,anodes,and cathodes bring about frequent accidents regarding battery fires and explosions and impede the development of high-performance SIBs.Therefore,safety analysis and high-safety battery design have become prerequisites for the development of advanced energy storage systems.The reported reviews that only focus on a specific issue are difficult to provide overall guidance for building high-safety SIBs.To overcome the limitation,this review summarizes the recent research progress from the perspective of key components of SIBs for the first time and evaluates the characteristics of various improvement strategies.By orderly analyzing the root causes of safety problems associated with different components in SIBs(including electrolytes,anodes,and cathodes),corresponding improvement strategies for each component were discussed systematically.In addition,some noteworthy points and perspectives including the chain reaction between security issues and the selection of improvement strategies tailored to different needs have also been proposed.In brief,this review is designed to deepen our understanding of the SIBs safety issues and provide guidance and assistance for designing high-safety SIBs.

Structure evolution of oxygen removal from porous carbon for optimizing supercapacitor performance

The presence of oxygen functional groups is detrimental to the capacitive performance of porous carbon electrode in organic electrolyte. In this regards, hydrogen thermal reduction has been demonstrated effective approach in removing the unstable surface oxygen while maintaining the high porosity of carbon matrix. However, the exact evolution mechanism of various oxygen species during this process, as well as the correlation with electrochemical properties, is still under development. Herein, biomass-based porous carbon is adopted as the model material to trace its structure evolution of oxygen removal under hydrogen thermal reduction process with the temperature range of 400–800 °C. The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700°C. XPS, TPRMS and Boehm titration results indicate that the oxygen elimination undergoes three distinctive stages(intermolecular dehydration, hydrogenation and decomposition reactions). The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700 °C. Benefiting from the stable electrochemical interface and the optimized porous structure, the as-obtained HAC-700 exhibit significantly suppressed self-discharge and leak current, with improved cycling stability, which is attributable to the stabilization of electrochemical interface between carbon surface and electrolyte. The result provides insights for rational design of surface chemistry for high-performance carbon electrode towards advanced energy storage.

Preparation of porous Mg electrode by electrodeposition

In order to obtain a porous Mg electrode with a stable skeleton, organic Mg fuel cell （OMFC）, the electrochemical behavior of Mg deposition on Cu and Ni metallic substrates in 1 mol/L EtMgBr/THF solution was investigated by SEM, EDS and electrochemical methods. The experimental results show that Mg can be electrodeposited on both substrates, as a continuous layer on a Cu substrate. Accordingly, an approach for producing a porous Mg electrode with a stable skeleton of OMFC was proposed by means of electrodeposition of Mg on a foamed Ni substrate with a layer of Cu pre-plating. The discharge performance of this porous Mg electrode of OMFC is superior to that of a planar Mg electrode.

Effect of Anodization Parameters on Morphologies of TiO2 Nanotube Arrays and Their Surface Properties

This work presents the potentiostatic anodization study of titania nanotube array films fabricated in fluoride-based organic electrolytes including DEG （diethylene glycol） and EG （ethylene glycol）. The work focuses on the effect of important anodization parameters such as applied voltage, anodization time, and electrolyte type on nanotube morphologies and corresponding surface properties. Depending upon unique nanotube formation structures obtained from each anodizing electrolyte, wettability of the nanotube array layer has been determined by means of the contact angle measurement. The EG nanotube array films with close-packing cell orientation are found to show hydrophilic behavior. While the well separated DEG nanotube array films are found to exhibit hydrophobic behavior, with the characteristics of more discrete, wider cell separation obtained through manipulating the electrolyte conditions and the fabrication techniques offering considerable prospects for developing the superhydrophobic sample surface. Such formation structures observed for the DEG fabricated nanotube is believed to play a prominent role in determining the surface wettability of the anodized nanotube array film. The achieved result in this work is anticipated to pave the way to other relevant applications, where interfacial properties are critically concerned.

Controlling Ion Conductance and Channels to Achieve Synapticlike Frequency Selectivity

Enhancing ion conductance and controlling transport pathway in organic electrolyte could be used to modulate ionic kinetics to handle signals. In a Pt/Poly(3-hexylthiophene-2,5-diyl)/Polyethylene?Li CF3SO3/Pt hetero-junction, the electrolyte layer handled at high temperature showed nano-fiber microstructures accompanied with greatly improved salt solubility. Ions with high mobility were confined in the nano-fibrous channels leading to the semiconducting polymer layer,which is favorable for modulating dynamic doping at the semiconducting polymer/electrolyte interface by pulse frequency.Such a device realized synaptic-like frequency selectivity, i.e., depression at low frequency stimulation but potentiation at high-frequency stimulation.

Electric Double layer Capacitor Based on Activated Carbon Material

In this study electric double layer capacitors (EDLCs) based on activated carbon material and organic electrolyte (tetraethyl ammonium tetrafluoroborate) were explored. The fabrication method for EDLC is presented and the performance of EDLC was examined by using the cyclic voltammetry, constant current charging and discharging technique, electrochemical impedance spectroscopy measurements. Influence of various components and design parameters on the performance of the capacitors were preliminarily investigated. Up to now, EDLC based on carbon materials can deliver 20.7 W/kg at the discharge rate of I =0.3 mA, together with the energy density of 8.5 Wh/kg. Equivalent series resistance (ESR) is 0.716 Ω·cm 2. The specific power of the capacitor is low and further attempts to raise the power capability of the capacitors are necessary. Some considerations are put forward to further improve the performance of EDLC.

Carbide derived carbon electrode with natural graphite addition in magnesium electrolyte based cell for supercapacitor enhancements

Herein,we have presented a supercapacitor based on carbide derived carbon（CDC） electrode with natural graphite（NG） addition.The capacitor was analyzed at 22°C by cyclic voltammetry,galvanostatic charge-discharge and impedance techniques using a 0.5 mol/L of magnesium（II）bis（trifluoro methanesulfonyl） imide（Mg TFSI） in ethylene carbonate-propylene carbonate（EC ：PC = 1 ：1,v/v） as electrolyte.The results conclude that the CDC cell enhancements have been proven by the composite electrode（5%–30% NG to CDC） especially on the cell efficiency and voltage i.e.,the CDC cell around 2.5 V limit was improved.An obtainable specific capacitance,real power and energy density are 15 F g-1,1.2 k W kg-1and 15 Wh kg-1,respectively.

Recent research progresses in ether-and ester-based electrolytes for sodium-ion batteries

Owing to the natural abundance and low cost of sodium resources,sodium-ion batteries(SIBs)have drawn considerable attention for state-of-the-art power storage devices over the last few years.To enable advanced SIBs with a brighter future,great effort has been made,not only through optimizing the electrode materials,but also with rationally designing various electrolyte systems.Among the available electrolyte systems,organic electrolytes,especially those based on esters as well as ethers,are the most promising ones for practical application in the foreseeable future,due to their numerous inherent advantages.This review is concerned with the recent research progresses on organic electrolytes for SIBs,focusing on etherbased and ester-based ones.

Controllable synthesis of well-ordered TiO_2 nanotubes in a mixed organic electrolyte for high-efficiency photocatalysis

Well-ordered TiO 2 nanotube arrays (TNAs) were fabricated by electrochemical anodization in a mixed organic electrolyte consisting of ethylene glycol and glycerol. The morphology, structure, crystalline phase, and photocatalytic properties of TNAs were characterized by using TEM, SEM, XRD and photodegradation of methylene blue. It was found that the morphology and structure of TNAs could be significantly influenced by the anodization time and applied voltage. The obtained tube length was found to be proportional to anodization time, and the calculated growth rate of nanotubes was 0.6 m/h. The microstructure analysis demonstrated that the diameter and thickness of the nanotubes increased with the increase of anodization voltage. The growth mechanism of TNAs was also proposed according to the observed relationship between current density and time during anodization. As expected, the obtained TNAs showed a higher photocatalytic activity than the commercial TiO 2 P25 nanoparticles.

Progress in electrolytes for beyond-lithium-ion batteries

The constant increase in global energy demand and stricter environmental standards are calling for advanced energy storage technologies that can store electricity from intermittent renewable sources such as wind,solar,and tidal power,to allow the broader implementation of the renewables.The gridoriented sodium-ion batteries,potassium ion batteries and multivalent ion batteries are cheaper and more sustainable alternatives to Li-ion,although they are still in the early stages of development.Additional optimisation of these battery systems is required,to improve the energy and power density,and to solve the safety issues caused by dendrites growth in anodes.Electrolyte,one of the most critical components in these batteries,could significantly influence the electrochemical performances and operations of batteries.In this review,the definitions and influences of three critical components(salts,solvents,and additives)in electrolytes are discussed.The significant advantages,challenges,recent progress and future optimisation directions of various electrolytes for monovalent and multivalent ions batteries(i.e.organic,ionic liquid and aqueous liquid electrolytes,polymer and inorganic solid electrolytes)are summarised to guide the practical application for grid-oriented batteries.

Carbon electrodes with ionophobic characteristics in organic electrolyte for high-performance electric double-layer capacitors

Activated carbon(AC)in organic electrolytebased electric double-layer capacitors(EDLCs)usually suffers from low specific capacitance.Most studies on AC focus on improving its surface area and optimizing pore structures to enhance its electrochemical performance in EDLCs.Unfortunately,the interfacial microenvironment,which is composed of nanoporous carbon and the organic electrolyte confined in it,is always ignored.Herein,a simple and powerful strategy to create AC with an ionophobic surface is proposed to address the poor efficiency of the electric doublelayer process.The polar C±F bonds formed in the AC material are characterized through near-edge X-ray absorption fine structure and X-ray photoelectron spectroscopy.The ionophobic characteristic of YP-F60 s in an organic electrolyte is extensively studied via contact angle measurements and smallangle X-ray scattering spectroscopy.An EDLC constructed with YP-F60 s as the electrode and 1 mol L^(-1) tetraethylammonium tetrafluoroborate/propylene carbonate as the electrolyte demonstrates high specific capacitance,low internal resistance,and excellent cycling stability.Our results successfully demonstrate the importance of the interfacial microenvironment of AC and its confined electrolyte to the electrochemical performance of EDLCs.Our work also offers new perspectives on the use of the CF;plasma technique to fabricate low-cost superior carbon for EDLCs.

High-performance organic electrolyte supercapacitors based on intrinsically powdery carbon aerogels

A novel class of powdery carbon aerogels（PCAs） has been developed by the union of microemulsion polymerization and hypercrosslinking, followed by carbonization. The resulting aerogels are in a microscale powdery form, demonstrate a well-defined 3D interconnected nanonetwork with hierarchical pores derived from numerous interstitial nanopores and intraparticle micropores, and exhibit high surface area（up to 1969 m^2/g）. Benefiting from these structural features, PCAs show impressive capacitive performances when utilized as electrodes for organic electrolyte supercapacitors,including large capacitances of up to 152 F/g, high energy densities of 37-15 Wh/kg at power densities of 34–6750 W/kg, and robust cycling stability.

Recent Advances in the Unconventional Design of Electrochemical Energy Storage and Conversion Devices

As the world works to move away from traditional energy sources,effective efficient energy storage devices have become a key factor for success.The emergence of unconventional electrochemical energy storage devices,including hybrid batteries,hybrid redox flow cells and bacterial batteries,is part of the solution.These alternative electrochemical cell configurations provide materials and operating condition flexibility while offering high-energy conversion efficiency and modularity of design-to-design devices.The power of these diverse devices ranges from a few milliwatts to several megawatts.Manufactur-ing durable electronic and point-of-care devices is possible due to the development of all-solid-state batteries with efficient electrodes for long cycling and high energy density.New batteries made of earth-abundant metal ions are approaching the capacity of lithium-ion batteries.Costs are being reduced with the advent of flow batteries with engineered redox molecules for high energy density and membrane-free power generating electrochemical cells,which utilize liquid dynamics and interfaces(solid,liquid,and gaseous)for electrolyte separation.These batteries support electrode regeneration strategies for chemical and bio-batteries reducing battery energy costs.Other batteries have different benefits,e.g.,carbon-neutral Li-CO_(2) batteries consume CO_(2) and generate power,offering dual-purpose energy storage and carbon sequestration.This work considers the recent technological advances of energy storage devices.Their transition from conventional to unconventional battery designs is examined to identify operational flexibilities,overall energy storage/conversion efficiency and application compatibility.Finally,a list of facilities for large-scale deployment of major electrochemical energy storage routes is provided.

Characterization and Thermodynamics of Al_2O_3-MnO-SiO_2(-MnS)Inclusion Formation in Carbon Steel Billet

A method to extract inclusion particles from solid steel by electrolysis with organic electrolyte solution was introduced; meanwhile, thermodynamics of inclusion formation was calculated using FaetSage software. The results showed that there were two kinds of inclusions in the billet, i.e. Al2O3-MnO-SiO2-MnS （AMS-MnS） and Al2O3- MnO-SiO2 （AMS）. Most of AMS-MnS inclusion particles, with diameter of 10--30 μm, showed three-layer structures： SiO2-rich core with a small quantity of Mn, intermediate AMS layer, and MnS outer layer containing small quanti- ties of A1 and O. Most AMS inclusion particles were 50--90 μm and exhibited homogeneous composition. Thermo- dynamic results indicated that SiO2-rich core could form firstly by Si reacting with O in molten steel at temperatures above 1 923 K during Si-Fe alloy addition, and then, the SiO2-rich core could react with Mn and Al to form liquid AMS enveloping the SiO2 rich core at 1823- 1873 K. MnS began to precipitate from AMS when temperature reached 1 728 K. Liquid AMS could form by coupled reaction among Si, Mn, Al and O in molten steel.

Multiple Functional Biomass-Derived Activated Carbon Materials for Aqueous Supercapacitors, Lithium-Ion Capacitors and Lithium-Sulfur Batteries

Biomass-derived activated carbon electrode materials have been synthesized by carbonization and KOH activa- tion processes from an agriculture waste - rice husk, composed of organic compound and silica. The surface area of activated carbon reached 1098.1 m2/g mainly including mesopores and macropores due to the template effect of sil- ica in rice husk. Owing to the existence of mesopores and macropores, the as-obtained activated carbon materials can be used in aqueous supercapacitors, lithium-ion （Li-ion） capacitors and lithium-sulfur （Li-S） batteries. In KOH electrolyte, fast rate performance （as high as 2 V/s） was obtained due to the existence of ideal electrical double layer capacitance. In organic electrolyte, high voltage （2.5 V） was achieved. Activated carbon electrode for Li-ion capac- itor also showed capacity of 17 mAh/g at 100 mA/g with the high voltage range of 2.5 V. The capacities of sul- fur-activated carbon in Li-S batteries were 1230 and 970 mAh/g at the current densities of 0.1 and 0.2 C. The pre- sent results showed that activated carbon materials with mesopores were good host to immobilize polysulfides.