Energy Materials

This study examines the performance of porous carbon as quasi-reference electrode (QRE) in aqueous media and evaluates their suitability. The performance of activated carbon and carbon black as QRE was investigated in acidic (H2SO4) and neutral (Na2SO4, NaCl, Li2SO4) solutions and compared to platinum metal wire and Ag/AgCl reference electrode. In neutral and acidic electrolyte, the porous carbon based QREs exhibited a notable stability and reliability with low level of potential drift (1 mV per day) and potential deviation of less than 10 mV. These results can contribute to the further development in porous carbon based QREs leading to novel opportunities in electrochemical analysis.

We introduce a high performance hybrid electrochemical energy storage system based on an aqueous electrolyte containing tin sulfate (SnSO4) and vanadyl sulfate (VOSO4) with nanoporous activated carbon. The energy storage mechanism of this system benefits from the unique synergy of concurrent electric double-layer formation, reversible tin redox reactions, and three-step redox reactions of vanadium. The hybrid system showed excellent electrochemical properties such as a promising energy capacity (ca. 75 W h kg-1, 30 W h L-1) and a maximum power of up to 1.5 kW kg-1 (600 W L-1, 250 W m-2), exhibiting capacitor-like galvanostatic cycling stability and a low level of self-discharging rate.

The electrochemical flow capacitor (EFC) is a novel design for supercapacitor technologies. To avoid misinterpretation arising from non-flow analytical methods, we have investigated an EFC system under continuous flow conditions. Several different surfactants were introduced as modifiers to activated carbon in an aqueous electrolyte with sodium sulfate (Na2SO4). A significant reduction in viscosity was found by adding sodium lignosulfonate, and as a consequence, a maximum volumetric capacitance of 26 F cm−3 was achieved for the EFC system. A steady performance of the EFC system was observed for 200 h in terms of the specific capacitance (90±5 F g−1); however, degradation in the power performance was observed. Membrane fouling was confirmed to be the major contributor to the power degradation, and a cleaning process using water was developed to partially restore the initial performance (≈70 %).

Herein the application of a recently introduced new method of tracking in-situ the intercalation-induced deformations of supercapacitor and Li-battery electrodes is reviewed. The method is based on the use of multi-harmonic electrochemical quartz microbalance with dissipation monitoring, EQCM-D (in-situ hydrodynamic spectroscopy) which enables a permanent control of the electrodes' state-of-health by probing their mechanical properties. The potential-dependent frequency and resonance width changes are fitted to a chosen hydrodynamic admittance model allowing thus quantification of the electrode deformations under different charging conditions. Intercalation of different alkaline metal cations into layered MXene electrode serves as a readily understandable working example of quantifying such electrodes deformations. Further method developments including in-situ viscoelastic characterization of composite porous electrodes are envisaged in the near future.

Capacitive deionization (CDI) is an emerging technology for the energy-efficient removal of dissolved ions from aqueous solutions. Expanding this technology to non-aqueous media, we present an experimental characterization of a pair of porous carbon electrodes towards electrosorption of dissolved ions in propylene carbonate. We demonstrate that application of CDI technology for treatment of an organic solution with an electrochemical stability window beyond 1.2 V allows for a higher salt removal capacity and higher charge efficiency as compared to CDI applied for treatment of aqueous electrolytes. Further, we show that using conductivity measurements of the stream emerging from the CDI cell combined with an equilibrium electric double-layer structure model, we can gain insights into charge compensation mechanisms and ion distribution in carbon nanopores.

Multiharmonic analysis by electrochemical quartz-crystal microbalance with dissipation monitoring (EQCM-D) is introduced as an excellent tool for quantitative studying electrosorption of ions from aqueous solution in mesoporous (BP-880) or mixed micro-mesoporous (BP-2000) carbon electrodes. Finding the optimal conditions for gravimetric analysis of the ionic content in the charged carbon electrodes, we propose a novel approach to modeling the charge-dependent gravimetric characteristics by incorporation of Gouy-Chapman-Stern electric double layer model for ions electrosorption into meso- and micro-mesoporous carbon electrodes. All three parameters of the gravimetric equation evaluated by fitting it to the experimental mass changes curves were validated using supplementary nitrogen gas sorption analysis and complementing atomic force microscopy. Important overlap between gravimetric EQCM-D analysis of the ionic content of porous carbon electrodes and the classical capacitive deionization models has been established. The necessity and usefulness of non-gravimetric EQCM-D characterizations of complex carbon architectures, providing insight into their unique viscoelastic behavior and porous structure changes, have been discussed in detail.

A primary atomic-scale effect accompanying Li-ion insertion into rechargeable battery electrodes is a significant intercalation-induced change of the unit cell volume of the crystalline material. This generates a variety of secondary multiscale dimensional changes and causes a deterioration in the energy storage performance stability. Although traditional in situ height-sensing techniques (atomic force microscopy or electrochemical dilatometry) are able to sense electrode thickness changes at a nanometre scale, they are much less informative concerning intercalation-induced changes of the porous electrode structure at a mesoscopic scale. Based on a electrochemical quartz-crystal microbalance with dissipation monitoring on multiple overtone orders, herein we introduce an in situ hydrodynamic spectroscopic method for porous electrode structure characterization. This new method will enable future developments and applications in the fields of battery and supercapacitor research, especially for diagnostics of viscoelastic properties of binders for composite electrodes and probing the micromechanical stability of their internal electrode porous structure and interfaces.

In this proof-of-concept study, we introduce and demonstrate MXene as a novel type of intercalation electrode for desalination via capacitive deionization (CDI). Traditional CDI cells employ nanoporous carbon electrodes with significant pore volume to achieve a large desalination capacity via ion electrosorption. By contrast, MXene stores charge by ion intercalation between the sheets of its two-dimensional nanolamellar structure. By this virtue, it behaves as an ideal pseudocapacitor, that is, showing capacitive electric response while intercalating both anions and cations. We synthesized Ti3C2-MXene by the conventional process of etching ternary titanium aluminum carbide i.e., the MAX phase (Ti3AlC2) with hydrofluoric acid. The MXene material was cast directly onto the porous separator of the CDI cell without added binder, and exhibited very stable performance over 30 CDI cycles with an average salt adsorption capacity of 13 +/- 2 mg g-1.

Performance stability in capacitive deionization (CDI) is particularly challenging in systems with a high amount of dissolved oxygen due to rapid oxidation of the carbon anode and peroxide formation. For example, carbon electrodes show a fast performance decay, leading to just 15% of the initial performance after 50 CDI cycles in oxygenated saline solution (5 mM NaCl). We present a novel strategy to overcome this severe limitation by employing nanocarbon particles hybridized with sol-gel-derived titania. In our proof-of-concept study, we demonstrate very stable performance in low molar saline electrolyte (5 mM NaCl) with saturated oxygen for the carbon/metal oxide hybrid (90% of the initial salt adsorption capacity after 100 cycles). The electrochemical analysis using a rotating disk electrode (RDE) confirms the oxygen reduction reaction (ORR) catalytic effect of FW200/TiO2, preventing local peroxide formation by locally modifying the oxygen reduction reaction.

This study presents electrospun niobium carbide/carbon (NbC/C) hybrid nanofibers, with an average diameter of 69 +/- 30 nm, as a facile precursor to derive either highly nanoporous niobium carbide-derived carbon (NbC-CDC) fibers for supercapacitor applications or niobium pentoxide/carbon (Nb2O5/C) hybrid fibers for battery-like energy storage. In all cases, the electrodes consist of binder-free and free-standing nanofiber mats that can be used without further conductive additives. Chlorine gas treatment conformally transforms NbC nanofiber mats into NbC-CDC fibers with a specific surface area of 1508 m2 g-1. These nanofibers show a maximum specific energy of 19.5 W h kg-1 at low power and 7.6 W h kg-1 at a high specific power of 30 kW kg-1 in an organic electrolyte. CO2 treatment transforms NbC into T-Nb2O5/C hybrid nanofiber mats that provide a maximum capacity of 156 mA h g-1. The presence of graphitic carbon in the hybrid nanofibers enabled high power handling, maintaining 50% of the initial energy storage capacity at a high rate of 10 A g-1 (64 C-rate). When benchmarked for an asymmetric full-cell, a maximum specific energy of 86 W h kg-1 was obtained. The high specific power for both systems, NbC-CDC and T-Nb2O5/C, resulted from the excellent charge propagation in the continuous nanofiber network and the high graphitization of the carbon structure.