Correlated surface-charging behaviors of two electrodes in an electrochemical cell.

It is revealed herein that surface-charging behaviors of the two electrodes constituting an electrochemical cell cannot be described independently by their respective electric double-layer (EDL) properties. Instead, they are correlated in such a way that the surface-charging behavior of each electrode is determined by the EDL and the reaction kinetics at both electrodes. Two fundamental equations describing the correlated surface-charging behaviors are derived, and approximate analytical solutions are obtained at low and high current densities, respectively, to facilitate transparent understanding. Important implications of the presented conceptual analysis for theoretical and computational electrochemistry are discussed. A strategy of modulating the activity of one electrode by tuning EDL parameters of the other in a two-electrode electrochemical cell is demonstrated.

Operando Nanoscale Imaging of Electrochemically Induced Strain in a Locally Polarized Pt Grain.

Developing new methods that reveal the structure of electrode materials under polarization is key to constructing robust structure-property relationships. However, many existing methods lack the spatial resolution in structural changes and fidelity to electrochemical operating conditions that are needed to probe catalytically relevant structures. Here, we combine a nanopipette electrochemical cell with three-dimensional X-ray Bragg coherent diffractive imaging to study how strain in a single Pt grain evolves in response to applied potential. During polarization, marked changes in surface strain arise from the Coulombic attraction between the surface charge on the electrode and the electrolyte ions in the electrochemical double layers, while the strain in the bulk of the crystal remains unchanged. The concurrent surface redox reactions have a strong influence on the magnitude and nature of the strain changes under polarization. Our studies provide a powerful blueprint to understand how structural evolution influences electrochemical performance at the nanoscale.

Switching Reaction Pathways of CO2 Electroreduction by Modulating Cations in the Electrochemical Double Layer.

Tuning the selectivity of CO2 electroreduction reaction (CO2RR) solely by changing electrolyte is a very attractive topic. In this study, we conducted CO2RR in different aqueous electrolytes over bulk metal electrodes. It was discovered that controlled CO2RR could be achieved by modulating cations in the electrochemical double layer. Specifically, ionic liquid cations in the electrolyte significantly inhibits the hydrogen evolution reaction (HER), while yielding high Faraday efficiencies toward CO (FECO) or formate (FEformate) depending on the alkali metal cations. For example, the product could be switched from CO (FECO=97.3 %) to formate (FEformate=93.5 %) by changing the electrolyte from 0.1 M KBr-0.5 M 1-octyl-3-methylimidazolium bromide (OmimBr) to 0.1 M CsBr-0.5 M OmimBr aqueous solutions over pristine Cu foil electrode. In situ spectroscopy and theoretical calculations reveal that the ordered structure generated by the assembly of Omim+ under an applied negative potential alters the hydrogen bonding structure of the interfacial water, thereby inhibiting the HER. The difference in selectivity in the presence of different cations is attributed to the hydrogen bonding effect caused by Omim+, which alters the solvated structure of the alkali metal cations and thus affects the stabilization of intermediates of different pathways.

Amine-aldehyde resin derived porous N-doped hollow carbon nanorods for high-energy capacitive energy storage.

Electrochemical double layer capacitors (EDLCs) are known for their high power density but hampered by low energy density. Herein, N-doped hollow carbon nanorods (NHCRs) have been constructed by a hard templating method using MnO2nanorods as the hard templates andm-phenylenediamine-formaldehyde resin as the carbon precursor. The NHCRs after activation (NHCRs-A) manifest abundant micropores/mesopores and an ultrahigh surface area (2166 m2g-1). When employed in ionic liquid (IL) electrolyte-based EDLCs, the NHCRs-A delivers a high specific capacitance (220 F g-1at 1 A g-1), an impressive energy density (110 Wh kg-1), and decent cyclability (97% retention over 15 000 cycles). The impressive energy density is derived from the abundant ion-available micropores, while the decent power density is originated from the hollow ion-diffusion channels as well as excellent wettability in ILs.In situinfrared spectroscopy together within situRaman unveil that both counter-ion adsorption and ion exchange are involved in the charge storage of NHCRs-A. This study provides insight into the construction of porous carbon materials for EDLCs.

Ag(e)ing and Degradation of Supercapacitors: Causes, Mechanisms, Models and Countermeasures.

The most prominent and highly visible advantage attributed to supercapacitors of any type and application, beyond their most notable feature of high current capability, is their high stability in terms of lifetime, number of possible charge/discharge cycles or other stability-related properties. Unfortunately, actual devices show more or less pronounced deterioration of performance parameters during time and use. Causes for this in the material and component levels, as well as on the device level, have only been addressed and discussed infrequently in published reports. The present review attempts a complete coverage on these levels; it adds in modelling approaches and provides suggestions for slowing down ag(e)ing and degradation.

Insight into the Effect of Glycerol on Dielectric Relaxation and Transport Properties of Potassium-Ion-Conducting Solid Biopolymer Electrolytes for Application in Solid-State Electrochemical Double-Layer Capacitor.

The increased interest in the transition from liquid to solid polymer electrolytes (SPEs) has driven enormous research in the area polymer electrolyte technology. Solid biopolymer electrolytes (SBEs) are a special class of SPEs that are obtained from natural polymers. Recently, SBEs have been generating much attention because they are simple, inexpensive, and environmentally friendly. In this work, SBEs based on glycerol-plasticized methylcellulose/pectin/potassium phosphate (MC/PC/K3PO4) are investigated for their potential application in an electrochemical double-layer capacitor (EDLC). The structural, electrical, thermal, dielectric, and energy moduli of the SBEs were analyzed via X-ray diffractometry (XRD), Fourier transforms infrared spectroscopy (FTIR), electrochemical impedance spectroscopy (EIS), transference number measurement (TNM), and linear sweep voltammetry (LSV). The plasticizing effect of glycerol in the MC/PC/K3PO4/glycerol system was confirmed by the change in the intensity of the samples' FTIR absorption bands. The broadening of the XRD peaks demonstrates that the amorphous component of SBEs increases with increasing glycerol concentration, while EIS plots demonstrate an increase in ionic conductivity with increasing plasticizer content owing to the formation of charge-transfer complexes and the expansion of amorphous domains in polymer electrolytes (PEs). The sample containing 50% glycerol has a maximal ionic conductivity of about 7.5 × 10-4 scm-1, a broad potential window of 3.99 V, and a cation transference number of 0.959 at room temperature. Using the cyclic voltammetry (CV) test, the EDLC constructed from the sample with the highest conductivity revealed a capacitive characteristic. At 5 mVs-1, a leaf-shaped profile with a specific capacitance of 57.14 Fg-1 was measured based on the CV data.

Engineering a Local Free Water Enriched Microenvironment for Surpassing Platinum Hydrogen Evolution Activity.

Manipulating the catalyst-electrolyte interface to push reactants into the inner Helmholtz plane (IHP) is highly desirable for efficient electrocatalysts, however, it has rarely been implemented due to the elusive electrochemical IHP and inherent inert catalyst surface. Here, we propose the introduction of local force fields by the surface hydroxyl group to engineer the electrochemical microenvironment and enhance alkaline hydrogen evolution activity. Taking a hydroxyl group immobilized Ni/Ni3 C heterostructure as a prototype, we reveal that the local hydrogen bond induced by the surface hydroxyl group drags 4-coordinated hydrogen-bonded H2 O molecules across the IHP to become free H2 O and thus continuously supply reactants forcatalytic sites catalytic sites. In addition, the hydroxyl group coupled with the Ni/Ni3 C heterostructure further lowers the water dissociation energy by polarization effects. As a direct outcome, hydroxyl-rich catalysts surpass Pt/C activity at high current density (500 mA cm-2 @ ≈276 mV) in alkaline medium.

Recent advances in process engineering and upcoming applications of metal-organic frameworks.

Progress in metal-organic frameworks (MOFs) has advanced from fundamental chemistry to engineering processes and applications, resulting in new industrial opportunities. The unique features of MOFs, such as their permanent porosity, high surface area, and structural flexibility, continue to draw industrial interest outside the traditional MOF field, both to solve existing challenges and to create new businesses. In this context, diverse research has been directed toward commercializing MOFs, but such studies have been performed according to a variety of individual goals. Therefore, there have been limited opportunities to share the challenges, goals, and findings with most of the MOF field. In this review, we examine the issues and demands for MOF commercialization and investigate recent advances in MOF process engineering and applications. Specifically, we discuss the criteria for MOF commercialization from the views of stability, producibility, regulations, and production cost. This review covers progress in the mass production and formation of MOFs along with future applications that are not currently well known but have high potential for new areas of MOF commercialization.

Role of FTFSI Anion Asymmetry on Physical Properties of AFTFSI (A=Li, Na and K) Based Electrolytes and Consequences on Supercapacitor Application.

This study compares the physicochemical properties of six electrolytes comprising of three salts: LiFTFSI, NaFTFSI and KFTFSI in two solvent mixtures, the binary (3EC/7EMC) and the ternary (EC/PC/3DMC). The transport properties (conductivity, viscosity) as a function of temperature and concentration were modeled using the extended Jones-Dole-Kaminsky equation, the Arrhenius model, and the Eyring theory of transition state for activated complexes. Results are discussed in terms of ionicity, solvation shell, and cross-interactions between electrolyte components. The application of the six formulated electrolytes in symmetrical activated carbon (AC)//AC supercapacitors (SCs) was characterized by cyclic voltammetry (CV), galvanostatic cycling with potential limitation (GCPL), electrochemical impedance spectroscopy (EIS) and accelerated aging. Results revealed that the geometrical flexibility of the FTFSI anion allows it to access and diffuse easily in AC whereas its counter ions (Li+ , Na+ or K+ ) can remain trapped in porosity. However, this drawback was partially resolved by mixing LiFTFSI and KFTFSI salts in the electrolyte.

The Study of Electrical and Electrochemical Properties of Magnesium Ion Conducting CS: PVA Based Polymer Blend Electrolytes: Role of Lattice Energy of Magnesium Salts on EDLC Performance.

Plasticized magnesium ion conducting polymer blend electrolytes based on chitosan (CS): polyvinyl alcohol (PVA) was synthesized with a casting technique. The source of ions is magnesium triflate Mg(CF3SO3)2, and glycerol was used as a plasticizer. The electrical and electrochemical characteristics were examined. The outcome from X-ray diffraction (XRD) examination illustrates that the electrolyte with highest conductivity exhibits the minimum degree of crystallinity. The study of the dielectric relaxation has shown that the peak appearance obeys the non-Debye type of relaxation process. An enhancement in conductivity of ions of the electrolyte system was achieved by insertion of glycerol. The total conductivity is essentially ascribed to ions instead of electrons. The maximum DC ionic conductivity was measured to be 1.016 × 10-5 S cm-1 when 42 wt.% of plasticizer was added. Potential stability of the highest conducting electrolyte was found to be 2.4 V. The cyclic voltammetry (CV) response shows the behavior of the capacitor is non-Faradaic where no redox peaks appear. The shape of the CV response and EDLC specific capacitance are influenced by the scan rate. The specific capacitance values were 7.41 F/g and 32.69 F/g at 100 mV/s and 10 mV/s, respectively. Finally, the electrolyte with maximum conductivity value is obtained and used as electrodes separator in the electrochemical double-layer capacitor (EDLC) applications. The role of lattice energy of magnesium salts in energy storage performance is discussed in detail.

Capacitive hysteresis at the 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)-trifluorophosphate-polycrystalline gold interface.

We report potential-dependent capacitance curves over a 2-V potential range for the 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)-trifluorophosphate (Emim FAP)-polycrystalline gold interface, and examine the effect of potential scan direction on results. We find very small levels of capacitive hysteresis in the Emim FAP-polycrystalline Au electrochemical system, where capacitance curves show minor dependence on the potential scan direction employed. This is a considerably different response than that reported for the Emim FAP-Au(111) interface where significant hysteresis is observed based on the potential scan direction (Drüschler et al. in J Phys Chem C 115 (14):6802-6808, 2011). Hysteresis effects have previously been suggested to be a general feature of an ionic liquid (IL) at electrified interfaces due to slow interfacial processes and has been demonstrated for numerous electrochemical systems. We provide new evidence that the experimental procedure used to acquire capacitance data and data workup could also have implications on capacitance-potential relationships in ILs. This work serves to progress our understanding of the nature of capacitive hysteresis at the IL-electrode interface. Graphical abstract Subtle changes in experimental methods can lead to significantly different capacitance measurements in ionic liquids. Which is the best approach?

Supercapacitive microbial desalination cells: New class of power generating devices for reduction of salinity content.

In this work, the electrodes of a microbial desalination cell (MDC) are investigated as the positive and negative electrodes of an internal supercapacitor. The resulting system has been named a supercapacitive microbial desalination cell (SC-MDC). The electrodes are self-polarized by the red-ox reactions and therefore the anode acts as a negative electrode and the cathode as a positive electrode of the internal supercapacitor. In order to overcome cathodic losses, an additional capacitive electrode (AdE) was added and short-circuited with the SC-MDC cathode (SC-MDC-AdE). A total of 7600 discharge/self-recharge cycles (equivalent to 44 h of operation) of SC-MDC-AdE with a desalination chamber filled with an aqueous solution of 30 g L-1 NaCl are reported. The same reactor system was operated with real seawater collected from Pacific Ocean for 88 h (15,100 cycles). Maximum power generated was 1.63 ±â€¯0.04 W m-2 for SC-MDC and 3.01 ±â€¯0.01 W m-2 for SC-MDC-AdE. Solution conductivity in the desalination reactor decreased by ∼50% after 23 h and by more than 60% after 44 h. There was no observable change in the pH during cell operation. Power/current pulses were generated without an external power supply.

Miniaturized supercapacitors: key materials and structures towards autonomous and sustainable devices and systems.

Supercapacitors (SCs) are playing a key role for the development of self-powered and self-sustaining integrated systems for different fields ranging from remote sensing, robotics and medical devices. SC miniaturization and integration into more complex systems that include energy harvesters and functional devices are valuable strategies that address system autonomy. Here, we discuss about novel SC fabrication and integration approaches. Specifically, we report about the results of interdisciplinary activities on the development of thin, flexible SCs by an additive technology based on Supersonic Cluster Beam Deposition (SCBD) to be implemented into supercapacitive electrolyte gated transistors and supercapacitive microbial fuel cells. Such systems integrate at materials level the specific functions of devices, like electric switch or energy harvesting with the reversible energy storage capability. These studies might open new frontiers for the development and application of new multifunction-energy storage elements.

Gaining insight into the impact of electronic property and interface electrostatic field on ORR kinetics in alloy engineering via theoretical prognostication and experimental validation.

Alloy engineering has been utilized as a potent strategy to modulate the oxygen reduction reaction （ORR） activity. However, the regulatory mechanism underpinning the ORR kinetics by means of alloy engineering is still shrouded in ambiguity. This work places emphasis on the kinetics of the ORR concerning Pt3M (M = Cr, Co, Cu, Pd, Sn, and Ir) catalysts, and integrates theoretical prognostication and experimental validation to illuminate the fundamental principles of alloy engineering. The ORR kinetic activity, as prognosticated by theory, shows significant agreement with experimental results, provided that the rate-determining step (RDS) accounts for a dominant role in the potential-independent kinetic mechanism. In essence, alloy engineering manipulates electronic properties through electron transfer to modulate intermediate adsorption and adjusts the interface electric field (Efield) to regulate hydrogen atom transport, ultimately influencing kinetics. The Efield holds greater significance in ORR kinetics compared to the intermediate adsorption (EadsO), the corresponding degrees of correlation with free energy barriers (Ea) of RDS are -0.89, and 0.75, respectively. This work highlights the nature of alloy engineering for ORR kinetics modulation and assists in the design of efficient catalysts.

A Comprehensive Formulation of Aqueous Electrolytes for Low-Temperature Supercapacitors.

Safer-by-design and sustainable energy storage devices are envisioned to be among the required 2.0 solutions to satisfy the fast growing energy demands. Responding to this evolution cannot be freed from a global and synergetic approach to design the requisite electrolytes taking into account the toxicity, the eco-compatibility and the cost of their constituents. To target low-temperature applications, a non-toxic and cost-efficient eutectic system comprising LiNO3 in water with 1,3-propylene glycol as co-solvent was selected to design a ternary electrolyte with a wide liquid range. By using this electrolyte in an electrochemical double-layer capacitor (EDLC), the operating voltage of the device reaches an optimum of 2.0 V at -40 °C over more than 100 h of floating. Moreover, after being set up at 20 °C, the temperature resilience of the capacitance is near total, demonstrating thus a promising feature related to the suitable thermal and electrochemical behaviours of the tested EDLC devices.

Impact of carbon pores size on ionic liquid based-supercapacitor performance.

A comprehensive comparison of symmetrical supercapacitors assembling carbon electrodes with exclusively microporous, mesoporous or combined micro-mesoporous networks provides a critical outlook on the influence of pores size on the performance with ionic liquid-based electrolyte 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIm-TFSI) dissolved in acetonitrile. Contrary to widespread claims, the results for an electrodes set involving carbons of different origin indicate that the presence of large pores does not ensure a better supercapacitor performance. At low current density, the capacitance is basically determined by the surface in pores above 0.8 nm, regardless of the pore size distribution. In addition, the beneficial effect of large pores on the response rate of the supercapacitor cannot be concluded in a straightforward manner. On the contrary, wide porosity in electrodes has detrimental effects that should not be underestimated as far as the competitiveness of the final device is concerned. The greater amount of electrolyte required by larger pores will increase both the weight and the cost of the cell. More importantly, the widening of carbon pores (even in the range of micropores) notably reduces the density of the corresponding electrodes and, consequently, the supercapacitor performance in volumetric terms may not be suitable for practical applications.

Characteristics of Plasticized Lithium Ion Conducting Green Polymer Blend Electrolytes Based on CS: Dextran with High Energy Density and Specific Capacitance.

The solution cast process is used to set up chitosan: dextran-based plasticized solid polymer electrolyte with high specific capacitance (228.62 F/g) at the 1st cycle. Fourier-transform infrared spectroscopy (FTIR) pattern revealed the interaction between polymers and electrolyte components. At ambient temperature, the highest conductive plasticized system (CDLG-3) achieves a maximum conductivity of 4.16 × 10-4 S cm-1. Using both FTIR and electrical impedance spectroscopy (EIS) methods, the mobility, number density, and diffusion coefficient of ions are measured, and they are found to rise as the amount of glycerol increases. Ions are the primary charge carriers, according to transference number measurement (TNM). According to linear sweep voltammetry (LSV), the CDLG-3 system's electrochemical stability window is 2.2 V. In the preparation of electrical double layer capacitor devices, the CDLG-3 system was used. There are no Faradaic peaks on the cyclic voltammetry (CV) curve, which is virtually rectangular. Beyond the 20th cycle, the power density, energy density, and specific capacitance values from the galvanostatic charge-discharge are practically constant at 480 W/Kg, 8 Wh/Kg, and 60 F g-1, for 180 cycles.

Carbon Nanotube Based Robust and Flexible Solid-State Supercapacitor.

All solid-state flexible electrochemical double-layer capacitors (EDLCs) are crucial for providing energy options in a variety of applications, ranging from wearable electronics to bendable micro/nanotechnology. Here, we report on the development of robust EDLCs using aligned multiwalled carbon nanotubes (MWCNTs) grown directly on thin metal foils embedded in a poly(vinyl alcohol)/phosphoric acid (PVA/H3PO4) polymer gel. The thin metal substrate holding the aligned MWCNT assembly provides mechanical robustness and the PVA/H3PO4 polymer gel, functioning both as the electrolyte as well as the separator, provides sufficient structural flexibility, without any loss of charge storage capacity under flexed conditions. The performance stability of these devices was verified by testing them under straight and bent formations. A high value of the areal specific capacitance (CSP) of ∼14.5 mF cm-2 with an energy density of ∼1 µW h cm-2 can be obtained in these devices. These values are significantly higher (in some cases, orders of magnitude) than several graphene as well as single-walled nanotube-based EDLC's utilizing similar electrolytes. We further show that these devices can withstand multiple (∼2500) mechanical bending cycles, without losing their energy storage capacities and are functional within the temperature range of 20 to 70 °C. Several strategies for enhancing the capacitive charge storage, such as physically stacking (in parallel) individual devices, or postproduction thermal annealing of electrodes, are also demonstrated. These findings demonstrated in this article provide tremendous impetus toward the realization of robust, stackable, and flexible all solid-state supercapacitors.

In Situ Fabrication of Activated Carbon from a Bio-Waste Desmostachya bipinnata for the Improved Supercapacitor Performance.

Herein, we demonstrate the fabrication of highly capacitive activated carbon (AC) using a bio-waste Kusha grass (Desmostachya bipinnata), by employing a chemical process followed by activation through KOH. The as-synthesized few-layered activated carbon has been confirmed through X-ray powder diffraction, transmission electron microscopy, and Raman spectroscopy techniques. The chemical environment of the as-prepared sample has been accessed through FTIR and UV-visible spectroscopy. The surface area and porosity of the as-synthesized material have been accessed through the Brunauer-Emmett-Teller method. All the electrochemical measurements have been performed through cyclic voltammetry and galvanometric charging/discharging (GCD) method, but primarily, we focus on GCD due to the accuracy of the technique. Moreover, the as-synthesized AC material shows a maximum specific capacitance as 218 F g-1 in the potential window ranging from - 0.35 to + 0.45 V. Also, the AC exhibits an excellent energy density of ~ 19.3 Wh kg-1 and power density of ~ 277.92 W kg-1, respectively, in the same operating potential window. It has also shown very good capacitance retention capability even after 5000th cycles. The fabricated supercapacitor shows a good energy density and power density, respectively, and good retention in capacitance at remarkably higher charging/discharging rates with excellent cycling stability. Henceforth, bio-waste Kusha grass-derived activated carbon (DP-AC) shows good promise and can be applied in supercapacitor applications due to its outstanding electrochemical properties. Herein, we envision that our results illustrate a simple and innovative approach to synthesize a bio-waste Kusha grass-derived activated carbon (DP-AC) as an emerging supercapacitor electrode material and widen its practical application in electrochemical energy storage fields.

Characteristics of a Plasticized PVA-Based Polymer Electrolyte Membrane and H+ Conductor for an Electrical Double-Layer Capacitor: Structural, Morphological, and Ion Transport Properties.

Poly (vinyl alcohol) (PVA)-based solid polymer electrolytes doped with ammonium thiocyanate (NH4SCN) and glycerol were fabricated using a solution casting method. Lithium-based energy storage devices are not environmentally friendly materials, and they are toxic. Thus, proton-conducting materials were used in this work as they are harmless and are smaller than lithium. The interaction between PVA and the electrolyte elements was shown by FTIR analysis. The highest conductivity of 1.82 × 10-5 S cm-1 was obtained by the highest-conducting plasticized system (PSP_2) at room temperature. The mobility, diffusion coefficient, and number density of anions and cations were found to increase with increasing glycerol. FESEM was used to investigate the influence of glycerol on film morphology. TNM showed that the cations and anions were the main charge carriers. LSV showed that the electrochemical stability window of the PSP_2 system was 1.99 V. The PSP_2 system was applied in the preparation of an electrical double layer capacitor device. The shape of the cyclic voltammetry (CV) curve was nearly rectangular with no Faradaic peaks. From the galvanostatic charge-discharge analysis, the power density, energy density, and specific capacitance values were nearly constant beyond the first cycle at 318.73 W/Kg, 2.06 Wh/Kg, and 18.30 F g-1, respectively, for 450 cycles.