Energie-Materialien

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.

In this study, carbide-derived carbon fibers from silicon oxycarbide precursor were synthesized by electrospinning of a commercially available silicone resin without adding a carrier polymer for the electrospinning process. The electrospun fibers were pyrolyzed yielding SiOC. Modifying the synthesis procedure, we were also able to obtain electrosprayed SiOC beads instead of fibers. After chlorine treatment, nanoporous carbon with a specific surface area of up to 2394 m2 g−1 was obtained (3089 m2 g−1 BET). Electrochemical characterization of the SiOC-CDC either as free-standing fiber mat electrodes or polymer-bound bead films was performed in 1 M tetraethylammonium tetrafluoroborate in acetonitrile (TEA-BF4 in ACN). The electrospun fibers presented a high gravimetric capacitance of 135 F g−1 at 10 mV s−1 and a very high power handling, maintaining 63% of the capacitance at 100 A g−1. Comparative data of SiOC-CDC beads and fibers show enhanced power handling for fiber mats only when the fiber network is intact, that is, a lowered performance was observed when using crushed mats that employ polymer binder.

Metallic lithium is the most widespread reference electrode in lithium ion battery research, but its high reactivity limits the usage primarily to conventional carbonate based electrolytes. Novel high power concepts, like hybrid supercapacitors, require lithium containing electrolytes with high ionic conductivity (e.g., acetonitrile), which are not always stable versus lithium. In the current work we face this issue by refining activated carbon as a quasi-reference electrode originally employed for conventional supercapacitors. Different commercially available carbon powders were examined as reference electrode materials and calibrated in lithium-salt containing acetonitrile versus Li+ intercalation/de-intercalation reaction of nanoparticulate Li4Ti5O12. The stability of the activated carbon reference electrode is highly affected by the salt employed and decreases in the following order: LiTFSI > LiClO4 > LiPF6 > LiBF4. Only a negligible impact of electrolyte solvent, pore size distribution and reference electrode binder was observed. Furthermore, activated carbon was functionalized (HNO3 treated) and de-functionalized (thermal annealing in vacuum or hydrogen) to investigate the impact of carbon functionalization on the reference electrode stability. Nitrogen and oxygen containing surface groups have been found to drastically improve long-term stability of activated carbon quasi-reference electrodes. Even after 15 days exposed to the electrolyte, the potential of HNO3 treated activated carbon is marginally altered by 10 mV.

A novel, two step synthesis is presented combining the formation of carbide-derived carbon (CDC) and redox-active vanadium pentoxide (V2O5) in a core-shell manner using solely vanadium carbide (VC) as the precursor. In a first step, the outer part of VC particles is transformed to nanoporous CDC owing to the in situ formation of chlorine gas from NiCl2 at 700 [degree]C. In a second step, the remaining VC core is calcined in synthetic air to obtain V2O5/CDC core-shell particles. Materials characterization by means of electron microscopy, Raman spectroscopy, and X-ray diffraction clearly demonstrates the partial transformation from VC to CDC, as well as the successive oxidation to V2O5/CDC core-shell particles. Electrochemical performance was tested in organic 1 M LiClO4 in acetonitrile using half- and asymmetric full-cell configuration. High specific capacities of 420 mA h g-1 (normalized to V2O5) and 310 mA h g-1 (normalized to V2O5/CDC) were achieved. The unique nanotextured core-shell architecture enables high power retention with ultrafast charging and discharging, achieving more than 100 mA h g-1 at 5 A g-1 (rate of 12C). Asymmetric cell design with CDC on the positive polarization side leads to a high specific energy of up to 80 W h kg-1 with a superior retention of more than 80% over 10 000 cycles and an overall energy efficiency of up to 80% at low rates.

Manganese oxide presents very promising electrochemical properties as an electrode material in supercapacitors, but there remain important open questions to guide further development of the complex manganese oxide/carbon/electrolyte system. Our work addresses specifically the influence of carbon ordering and the difference between outer and inner porosity of carbon particles for the application in aqueous 1 M Na2SO4 and 1 M LiClO4 in acetonitrile. Birnessite-type manganese oxide was hydrothermally hybridized on two kinds of carbon onions with only outer surface area and different electrical conductivity, and conventional activated carbon with a high inner porosity. Carbon onions with a high degree of carbon ordering, high conductivity, and high outer surface area were identified as the most promising material, yielding 179 F g-1. Pore blocking in activated carbon yields unfavorable electrochemical performances. The highest specific energy of 16.4 W h kg-1 was measured for a symmetric full-cell arrangement of manganese oxide coated high temperature carbon onions in the organic electrolyte. High stability during 10 000 cycles was achieved for asymmetric full-cells, which proved as a facile way to enhance the electrochemical performance stability.