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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.
Redox-electrolytes for non-flow electrochemical energy storage: A critical review and best practice
(2019)
Over recent decades, a new type of electric energy storage system has emerged with the principle that the electric charge can be stored not only at the interface between the electrode and the electrolyte but also in the bulk electrolyte by redox activities of the electrolyte itself. Those redox electrolytes are promising for non-flow hybrid energy storage systems, or redox electrolyte-aided hybrid energy storage (REHES) systems; particularly, when they are combined with highly porous carbon electrodes. In this review paper, critical design considerations for the REHES systems are discussed as well as the effective electrochemical characterization techniques. Appropriate evaluation of the electrochemical performance is discussed thoroughly, including advanced analytical techniques for the determination of the electrochemical stability of the redox electrolytes and self-discharge rate. Additionally, critical summary tables for the recent progress on REHES systems are provided. Furthermore, the unique synergistic combination of porous carbon materials and redox electrolytes is introduced in terms of the diffusion, adsorption, and electrochemical kinetics modulating energy storage in REHES systems.
A successful transition from fossil to renewable energy sources requires electrochemical energy storage devices that surpass current lithium-ion battery technology in specific power and performance stability. In this PhD thesis, hybrid materials containing carbon and metal oxide components are synthesized, and hybrid cell architectures employing both a Faradaic and a capacitive electrode are explored. For material hybridization, atomic layer deposition is used to deposit nanoscopic layers of metal oxide on carbon substrates. This strategy allows to combine the high capacity of Faradaic reactions with the high power enabled by the large electrode-electrolyte interface. The porosity of the carbon substrate plays a major role in the resulting electrochemical performance; ideal carbon substrates show internal mesopores (2 50 nm). Hybrid supercapacitor devices are optimized by using these hybrid materials as the cell's Faradaic electrode. It is demonstrated that the kinetics and overpotentials of the Faradaic reactions are the determining factors to enable fast and efficient cell performance. Finally, the specific energy of hybrid supercapacitor cells is drastically increased by using lithium- or sodium-containing ionic liquid electrolyte. This novel concept increases the accessible cell voltage, operation temperature window, and safety of the hybrid supercapacitor cell.
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.
In this study, we explore carbon onions (diameter below 10 nm), for the first time, as a substrate material for lithium sulfur cathodes. We introduce several scalable synthesis routes to fabricate carbon onion-sulfur hybrids by adopting in situ and melt diffusion strategies with sulfur fractions up to 68 mass%. The conducting skeleton of agglomerated carbon onions proved to be responsible for keeping active sulfur always in close vicinity to the conducting matrix. Therefore, the hybrids are found to be efficient cathodes for Li-S batteries, yielding 97-98% Coulombic efficiency over 150 cycles with a slow fading of the specific capacity (ca. 660 mA h g-1 after 150 cycles) in long term cycle test and rate capability experiments.
This work presents the synthesis of MoO2/MoS2 core/shell nanoparticles within a carbon nanotube network and their detailed electron microscopy investigation in up to three dimensions. The triple-hybrid core/shell material was prepared by atomic layer deposition of molybdenum oxide onto carbon nanotube networks, followed by annealing in a sulfur-containing gas atmosphere. High-resolution transmission electron microscopy together with electron diffraction, supported by chemical analysis via energy dispersive X-ray and electron energy loss spectroscopy, gave proof of a MoO2 core covered by few layers of a MoS2 shell within an entangled network of carbon nanotubes. To gain further insights into this complex material, the analysis was completed with 3D electron tomography. By using Z-contrast imaging, distinct reconstruction of core and shell material was possible, enabling the analysis of the 3D structure of the material. These investigations showed imperfections in the nanoparticles which can impact material performance, i.e. for faradaic charge storage or electrocatalysis.
Atomic layer deposition has proven to be a particularly attractive approach for decorating mesoporous carbon substrates with redox active metal oxides for electrochemical energy storage. This study, for the first time, capitalizes on the cyclic character of atomic layer deposition to obtain a highly conformal and atomically controlled decoration of carbon onions with alternating stacks of vanadia and titania. The addition of 25 mass% TiO2 leads to an expansion of the VO2 unit cell, thus greatly enhancing lithium intercalation capacity and kinetics. Electrochemical characterization revealed ultrahigh discharge capacity of up to 382 mAh[middle dot]g-1 of the composite electrode (554 mAh[middle dot]g-1 per metal oxide) with an impressive capacity retention of 82 mAh[middle dot]g-1 (120 mAh[middle dot]g-1 per metal oxide) at a high discharge rate of 20 A[middle dot]g-1 or 52 C. Rigorous stability benchmarking showed superior stability over 3,000 cycles when discharging to a reduced potential of -1.8 V vs. carbon. These capacity values are among the highest reported for any metal oxide system, while in addition, supercapacitor-like power performance and longevity are achieved. On a device level, high specific energy and power of up to 110 Wh[middle dot]kg-1 and 6 kW[middle dot]kg-1, respectively, were achieved when employing the hybrid material as anode versus activated carbon cathode.
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.
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.
MXene as a novel intercalation-type pseudocapacitive cathode and anode for capacitive deionization
(2016)
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.
