Energy Materials

The structural characterisation of nanoporous carbons is a challenging task as they generally lack long-range order and can exhibit diverse local structures. Such characterisation represents an important step towards understanding and improving the properties and functionality of porous carbons, yet few experimental techniques have been developed for this purpose. Here we demonstrate the application of nuclear magnetic resonance (NMR) spectroscopy and pair distribution function (PDF) analysis as new tools to probe the local structures of porous carbons, alongside more conventional Raman spectroscopy. Together, the PDFs and the Raman spectra allow the local chemical bonding to be probed, with the bonding becoming more ordered for carbide-derived carbons (CDCs) synthesised at higher temperatures. The ring currents induced in the NMR experiment (and thus the observed NMR chemical shifts for adsorbed species) are strongly dependent on the size of the aromatic carbon domains. We exploit this property and use computer simulations to show that the carbon domain size increases with the temperature used in the carbon synthesis. The techniques developed here are applicable to a wide range of porous carbons, and offer new insights into the structures of CDCs (conventional and vacuum-annealed) and coconut shell-derived activated carbons.

Thermal energy is abundantly available, and especially low-grade heat is often wasted in industrial processes as a by-product. Tapping into this vast energy reservoir with cost-attractive technologies may become a key element for the transition to an energy-sustainable economy and society. We propose a novel heat-to-current converter which is based on the temperature dependence of the cell voltage of charged supercapacitors. Using a commercially available supercapacitor, we observed a thermal cell-voltage rise of around 0.6 mV K-1 over a temperature window of 0 [degree]C to 65 [degree]C. Within our theoretical model, this can be used to operate a Stirling-like charge-voltage cycle whose efficiency is competitive to the most-efficient thermoelectric (Seebeck) engines. Our proposed heat-to-current converter is built from cheap materials, contains no moving parts, and could operate with a plethora of electrolytes which can be chosen for optimal performance at specific working temperatures. Therefore, this heat-to-current converter is interesting for small-scale, domestic, and industrial applications.

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 ([small tau] = 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.

A 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 m2/g), and large micro/mesopore volume (up to 1.67 cm3/g). 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) and organic 1 M tetraethylammonium tetrafluoroborate in acetonitrile (130 F/g).

Microporous carbons are an interesting material for electrochemical applications. In this study, we evaluate several such carbons without/with N or S doping with regard to capacitive deionization. For this purpose, we extent the salt-templating synthesis towards biomass precursors and S-doped microporous carbons. The sample with the largest specific surface area (2830 m2 g−1) showed 1.0 wt % N and exhibited a high salt-sorption capacity of 15.0 mg g−1 at 1.2 V in 5 mM aqueous NaCl. While being a promising material from an equilibrium performance point of view, our study also gives first insights to practical limitations of heteroatom-doped carbon materials. We show that high heteroatom content may be associated with a low charge efficiency. The latter is a key parameter for capacitive deionization and is defined as the ratio between the amounts of removed salt molecules and electrical charge.

Dispersions of multi-wall carbon nanotubes, onion-like carbon, and nanodiamonds in ethylene glycol are produced using a homogenizer and an ultrasonic bath, altering the treatment time. The dispersed particles are then used as reinforcement phase for nickel matrix composites. These nanoparticles are chosen to represent different carbon hybridization states (sp2 vs. sp3) or a different particle geometry (0D vs. 1D). This allows for a systematic investigation of the effect of named differences on the dispersibility in the solvent and in the composite, as well as the mechanical reinforcement effect. A comprehensive suite of complementary analytical methods are employed, including transmission electron microscopy, Raman spectroscopy, dynamic light scattering, sedimentation analysis, zeta-potential measurements, scanning electron microscopy, electron back scatter diffraction, and Vickers microhardness measurements. It can be concluded that the maximum achievable dispersion grade in the solvent is similar, not altering the structural integrity of the particles. However, nanodiamonds show the best dispersion stability, followed by onion-like carbon, and finally multi-walled carbon nanotubes. The distribution and agglomerate sizes of the particles within the composites are in good agreement with the dispersion analysis, which is finally correlated with a maximum grain refinement by a factor of 3 and a maximum mechanical reinforcement effect for nanodiamonds.

Reversible Li-ion intercalation into composite Li-ion battery (LIB) electrodes is often accompanied by significant dimensional electrode changes (deformation) resulting in significant deterioration of the cycling performance. Viscoelastic properties of polymeric binders affected by intercalation-induced deformation of composite LIB electrodes have never been probed in situ on operating electrochemical cells. Here, we introduce a newly developed noninvasive method, namely electrochemical quartz-crystal microbalance with dissipation monitoring (EQCM-D), for in situ monitoring of elastic properties of polymeric binders during charging of LIB electrodes. As such, we find EQCM-D as a uniquely suitable tool to track the binder’s structural rigidity/softness in composite Li insertion electrodes in real-time by the characteristic increase/decrease of the dissipation factor during the charging-discharging process. The binders partially swollen in aprotic solutions demonstrate intermediate viscoelastic charge-rate-dependent behavior, revealing rigid/soft behavior at high/low charging rates, respectively. The method can be adjusted for continuous monitoring of elastic properties of the polymeric binders over the entire LIB electrodes cycling life.

Reversible Li-ion intercalation into composite Li-ion battery (LIB) electrodes is often accompanied by significant dimensional electrode changes (deformation) resulting in significant deterioration of the cycling performance. Viscoelastic properties of polymeric binders affected by intercalation-induced deformation of composite LIB electrodes have never been probed in-situ on operating electrochemical cells. Here, we introduce a newly developed noninvasive method, namely electrochemical quartz-crystal microbalance with dissipation monitoring (EQCM-D), for in-situ monitoring of elastic properties of polymeric binders during charging of LIB electrodes. As such, we find EQCM-D as a uniquely suitable tool to track the binder’s structural rigidity/softness in composite Li insertion electrodes in real-time by the characteristic increase/decrease of the dissipation factor during the charging-discharging process. The binders partially swollen in aprotic solutions demonstrate intermediate viscoelastic charge-rate-dependent behavior, revealing rigid/soft behavior at high/low charging rates, respectively. The method can be adjusted for continuous monitoring of elastic properties of the polymeric binders over the entire LIB electrodes cycling life.

Defects and impurities in carbon nanotubes (CNTs), inherent to all synthesis routes, are generally addressed by thermal and/or chemical post treatments. These require atmosphere control, time-consuming temperature ramping, chemical handling, and often incur further defects. Furthermore, certain applications require nanotube treatments, such as dispersion, that cause further unwanted damage. Laser radiation was found to drastically increase purity, crystallinity and mean inter-defect distance while reducing defects, as indicated by Raman spectroscopy, effectively annealing our single-wall CNTs. Laser power density and radiation times, in other words, fluence, were optimised. When applied to CNTs with mechanically induced defects, these were almost fully eliminated. In addition to the tuned annealing of CNTs, unintentional sample modification can occur during Raman measurements if the influence of the power density and the exposure time are underestimated or disregarded. Fast laser radiation times and simple manipulation outdo common purification treatments. Additionally, selective shape and site-specific parameters come into play such as interference patterns. Such arrangements of alternating tube quality, that is, in a CNT mat, could be interesting for preferred electronic conduction paths and find applications in, for example, interdigitated electrodes or sensors.