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- ItemCarbons and electrolytes for advanced supercapacitors(Hoboken, NJ : Wiley, 2014) Presser, VolkerElectrical energy storage (EES) is one of the most critical areas of technological research around the world. Storing and efficiently using electricity generated by intermittent sources and the transition of our transportation fleet to electric drive depend fundamentally on the development of EES systems with high energy and power densities. Supercapacitors are promising devices for highly efficient energy storage and power management, yet they still suffer from moderate energy densities compared to batteries. To establish a detailed understanding of the science and technology of carbon/carbon supercapacitors, this review discusses the basic principles of the electrical double-layer (EDL), especially regarding the correlation between ion size/ion solvation and the pore size of porous carbon electrodes. We summarize the key aspects of various carbon materials synthesized for use in supercapacitors. With the objective of improving the energy density, the last two sections are dedicated to strategies to increase the capacitance by either introducing pseudocapacitive materials or by using novel electrolytes that allow to increasing the cell voltage. In particular, advances in ionic liquids, but also in the field of organic electrolytes, are discussed and electrode mass balancing is expanded because of its importance to create higher performance asymmetric electrochemical capacitors.
- ItemEnhanced electrochemical energy storage by nanoscopic decoration of endohedral and exohedral carbon with vanadium oxide via atomic layer deposition(Washington D.C. : American Chemical Society, 2016) Fleischmann, Simon; Jäckel, Nicolas; Zeiger, Marco; Krüner, Benjamin; Grobelsek, Ingrid; Formanek, Petr; Choudhury, Soumyadip; Weingarth, Daniel; Presser, VolkerAtomic layer deposition (ALD) is a facile process to decorate carbon surfaces with redox-active nanolayers. This is a particularly attractive route to obtain hybrid electrode materials for high performance electrochemical energy storage applications. Using activated carbon and carbon onions as representatives of substrate materials with large internal or external surface area, respectively, we have studied the enhanced energy storage capacity of vanadium oxide coatings. While the internal porosity of activated carbon readily becomes blocked by obstructing nanopores, carbon onions enable the continued deposition of vanadia within their large interparticle voids. Electrochemical benchmarking in lithium perchlorate in acetonitrile (1 M LiClO4) showed a maximum capacity of 122 mAh/g when using vanadia coated activated carbon and 129 mAh/g for vanadia coated carbon onions. There is an optimum amount of vanadia between 50 and 65 wt % for both substrates that results in an ideal balance between redox-activity and electrical conductivity of the hybrid electrode. Assembling asymmetric (charge balanced) full-cells, a maximum specific energy of 38 Wh/kg and 29 Wh/kg was found for carbon onions and activated carbon, respectively. The stability of both systems is promising, with a capacity retention of ∼85–91% after 7000 cycles for full-cell measurements.
- ItemOne-step synthesis of nanocrystalline transition metal oxides on thin sheets of disordered graphitic carbon by oxidation of MXenes(Cambridge : Royal Society of Chemistry, 2014) Naguib, Michael; Mashtalir, Olhar; Lukatskaya, Maria R.; Dyatkin, Boris; Zhang, Chuanfang; Presser, Volker; Gogotsi, Yuri; Barsoum, Michael W.Herein we show that heating 2D Ti3C2 in air results in TiO2 nanocrystals enmeshed in thin sheets of disordered graphitic carbon structures that can handle extremely high cycling rates when tested as anodes in lithium ion batteries. Oxidation of 2D Ti3C2 in either CO2 or pressurized water also resulted in TiO2–C hybrid structures. Similarly, other hybrids can be produced, as we show here for Nb2O5/C from 2D Nb2C.
- ItemVanadia–titania multilayer nanodecoration of carbon onions via atomic layer deposition for high performance electrochemical energy storage(Cambridge : Royal Society of Chemistry, 2016) Fleischamann, Simon; Tolosa, Aura; Zieger, Marco; Krüner, Benjamin; Peter, Nicolas J.; Grobelsek, Ingrid; Quade, Antje; Kruth, Angela; Presser, VolkerAtomic layer deposition has proven to be a particularly attractive approach for ecorating mesoporous carbon substrates with redox active metal oxides for lectrochemical energy storage. This study, for the first time, capitalizes on the cyclic character of atomic layer deposition to obtain highly conformal and atomically controlled decoration of carbon onions with alternating stacks of vanadia and titania. The addition of 25 mass% TiO2 leads to expansion of the VO2 unit cell, thus greatly enhancing lithium intercalation capacity and kinetics. Electrochemical characterization revealed an ultrahigh discharge capacity of up to 382 mA h g^-1 of the composite electrode (554 mA h g^-1 per metal oxide) with an impressive capacity retention of 82 mA h g^-1 (120 mA h g^-1 per metal oxide) at a high discharge rate of 20 A g^-1 or 52C. Stability benchmarking showed stability over 3000 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, upercapacitor-like power performance and longevity are achieved. At a device level, high specific energy and power of up to 110 W h kg^-1 and 6 kW kg^-1, respectively, were achieved when employing the hybrid material as anode versus activated carbon cathode.
- ItemThermal conductivity and temperature profiles in carbon electrodes for supercapacitors(Amsterdam : Elsevier, 2014) Burheim, Odne S.; Aslan, Mesut; Atchison, Jennifer S.; Presser, VolkerThe thermal conductivity of supercapacitor film electrodes composed of activated carbon (AC), AC with 15 mass% multi-walled carbon nanotubes (MWCNTs), AC with 15 mass% onion-like carbon (OLC), and only OLC, all mixed with polymer binder (polytetrafluoroethylene), has been measured. This was done for dry electrodes and after the electrodes have been saturated with an organic electrolyte (1 M tetraethylammonium-tetrafluoroborate in acetonitrile, TEA-BF4). The thermal conductivity data was implemented in a simple model of generation and transport of heat in a cylindrical cell supercapacitor systems. Dry electrodes showed a thermal conductivity in the range of 0.09-0.19 W K-1 m-1 and the electrodes soaked with an organic electrolyte yielded values for the thermal conductivity between 0.42 and 0.47 W K-1 m-1. It was seen that the values related strongly to the porosity of the carbon electrode materials. Modeling of the internal temperature profiles of a supercapacitor under conditions corresponding to extreme cycling demonstrated that only a moderate temperature gradient of several degrees Celsius can be expected and which depends on the ohmic resistance of the cell as well as the wetting of the electrode materials.
- ItemAn electrochemical in situ study of freezing and thawing of ionic liquids in carbon nanopores(Cambridge : Royal Society of Chemistry, 2014) Weingarth, Daniel; Drumm, Robert; Foelske-Schmitz, Annette; Kotz, Rüdiger; Presser, VolkerRoom temperature ionic liquids (RTILs) are an emerging class of electrolytes enabling high cell voltages and, in return, high energy density of advanced supercapacitors. Yet, the low temperature behavior, including freezing and thawing, is little understood when ions are confined in the narrow space of nanopores. This study shows that RTILs may show a tremendously different thermal behavior when comparing bulk with nanoconfined properties as a result of the increased surface energy of carbon pore walls. In particular, a continuous increase in viscosity is accompanied by slowed-down charge-discharge kinetics as seen with in situ electrochemical characterization. Freezing reversibly collapses the energy storage ability and thawing fully restores the initial energy density of the material. For the first time, a different thermal behavior in positively and negatively polarized electrodes is demonstrated. This leads to different freezing and melting points in the two electrodes. Compared to bulk, RTILs in the confinement of electrically charged nanopores show a high affinity for supercooling; that is, the electrode may freeze during heating.
- ItemEmulsion soft templating of carbide-derived carbon nanospheres with controllable porosity for capacitive electrochemical energy storage(Cambridge : Royal Society of Chemistry, 2015) Oschatz, Martin; Zeiger, Marco; Jaeckel, Nicolas; Strubel, Patrick; Borchardt, Lars; Reinhold, Romy; Nickel, Winfried; Eckert, Jürgen; Presser, Volker; Kaskel, StefanA new approach to produce carbide-derived carbon nanospheres of 20-200 nm in diameter based on a novel soft-templating technique is presented. Platinum catalysis is used for the cross-linking of liquid (allylhydrido)polycarbosilane polymer chains with para-divinylbenzene within oil-in-water miniemulsions. Quantitative implementation of the pre-ceramic polymer can be achieved allowing precise control over the resulting materials. After pyrolysis and high-temperature chlorine treatment, resulting particles offer ideal spherical shape, very high specific surface area (up to 2347 m^2/g^-1), and large micro/mesopore volume (up to 1.67 cm^3/g^-1). The internal pore structure of the nanospheres is controllable by the composition of the oil phase within the miniemulsions. The materials are highly suitable for electrochemical double-layer capacitors with high specific capacitances in aqueous 1 M Na2SO4 solution (110 F/g^-1) and organic 1 M tetraethylammonium tetrafluoroborate in acetonitrile (130 F/g^-1).
- ItemCarbon flow electrodes for continuous operation of capacitive deionization and capacitive mixing energy generation(Cambridge : Royal Society of Chemistry, 2014) Porada, S.; Weingarth, Daniel; Hamelers, H.V.M.; Bryjak, M.; Presser, Volker; Biesheuvel, P.M.Capacitive technologies, such as capacitive deionization and energy harvesting based on mixing energy (“capmix” and “CO2 energy”), are characterized by intermittent operation: phases of ion electrosorption from the water are followed by system regeneration. From a system application point of view, continuous operation has many advantages, to optimize performance, to simplify system operation, and ultimately to lower costs. In our study, we investigate as a step towards second generation capacitive technologies the potential of continuous operation of capacitive deionization and energy harvesting devices, enabled by carbon flow electrodes using a suspension based on conventional activated carbon powders. We show how the water residence time and mass loading of carbon in the suspension influence system performance. The efficiency and kinetics of the continuous salt removal process can be improved by optimizing device operation, without using less common or highly elaborate novel materials. We demonstrate, for the first time, continuous energy generation via capacitive mixing technology using differences in water salinity, and differences in gas phase CO2 concentration. Using a novel design of cylindrical ion exchange membranes serving as flow channels, we continuously extract energy from available concentration differences that otherwise would remain unused. These results may contribute to establishing a sustainable energy strategy when implementing energy extraction for sources such as CO2-emissions from power plants based on fossil fuels.
- ItemA high-rate aqueous symmetric pseudocapacitor based on highly graphitized onion-like carbon/ barnessite-type manganese oxide nanohybrids(Cambridge : Royal Society of Chemistry, 2015) Makgopa, Katlego; Ejikeme, Paul M.; Jafta, Charl J.; Raju, Kumar; Zeiger, Marco; Presser, Volker; Ozoemena, Kenneth I.We present a study on the pseudocapacitive properties of birnessite-type MnO2 grafted on highly graphitized onion-like carbon (OLC/MnO2). In a three-electrode setup, we evaluated two different substrates, namely a platinum disc and nickel foam. The OLC/MnO2 nanohybrid exhibited a large specific capacitance (Csp) of 295 and 323 F g−1 (at 1 A g−1) for the Pt disc and Ni foam, respectively. In addition, the Ni foam substrate exhibited much higher rate capability (power density) than the Pt disc. A symmetrical two-electrode device, fabricated with the Ni foam, showed a large Csp of 254 F g−1, a specific energy density of 5.6 W h kg−1, and a high power density of 74.8 kW kg−1. These values have been the highest for onion-based electrodes so far. The device showed excellent capacity retention when subjected to voltage-holding (floating) experiments for 50 h. In addition, the device showed a very short time constant (τ = 40 ms). This high rate handling ability of the OLC/MnO2 nanohybrid, compared to literature reports, promises new opportunities for the development of aqueous-based pseudocapacitors.
- ItemEnhanced capacitance of nitrogen-doped hierarchically porous carbide-derived carbon in matched ionic liquids(Cambridge : Royal Society of Chemistry, 2015) Ewert, Julia K.; Weingarth, Daniel; Denner, Christine; Friedrich, Martin; Zeiger, Marco; Schreiber, Anna; Jäckel, Nicolas; Presser, Volker; Kempe, RhettSupercapacitors combine efficient electrical energy storage and performance stability based on fast electrosorption of electrolyte ions at charged interfaces. They are a central element of existing and emerging energy concepts. A better understanding of capacitance enhancement options is essential to exploit the full potential of supercapacitors. Here, we report a novel hierarchically structured N-doped carbon material and a significant capacitance enhancement for a specific ionic liquid. Our studies indicate that matching of the electrode material and the ionic liquid specifically leads to a constant normalized resistance of the electrode material (voltage window up to ±1 V vs. carbon) and a significant enhancement of the specific capacitance. Such effects are not seen for standard organic electrolytes, non-matched ionic liquids, or non-N-doped carbons. A higher N-doping of the electrode material improves the symmetric full cell capacitance of the match and considerably increases its long-term stability at +3 V cell voltage. This novel observance of enhanced specific capacitance for N-doped carbons with matched ionic liquid may enable a new platform for developing supercapacitors with enhanced energy storage capacity.