Edel Sheridan

Geometrically confined favourable ion packing for high gravimetric capacitance in carbon–ionic liquid supercapacitors

A supercapacitor, a safe and durable electrical energy storage device with fast charge–discharge capability, will achieve more widespread use if the specific energy can be improved. However, current understanding of pore characteristic effects on gravimetric capacitance has limited the development of electrode materials. We derive a model of ion packing in cylindrical nanopores, and it quantitatively reveals the significant impact of pore geometric characteristics on the gravimetric capacitance in neat ionic liquid, which is confirmed experimentally using a series of sponge-like carbons (carbon nanosponge). With the favourable ion packing proposed by the model, the electrode using the carbon nanosponge as an active material delivered double-layer capacitances of 290 F g−1 (20 °C) and 387 F g−1 (60 °C) with an operating cell voltage of 4 V. This study also provides systematical strategies for rational design of various carbon materials and ionic liquids by optimized ion packing for ultrahigh gravimetric capacitance.

Selective Charging Behavior in an Ionic Mixture Electrolyte-Supercapacitor System for Higher Energy and Power

Ion-ion interactions in supercapacitor (SC) electrolytes are considered to have significant influence over the charging process and therefore the overall performance of the SC system. Current strategies used to weaken ionic interactions can enhance the power of SCs, but consequently, the energy density will decrease due to the increased distance between adjacent electrolyte ions at the electrode surface. Herein, we report on the simultaneous enhancement of the power and energy densities of a SC using an ionic mixture electrolyte with different types of ionic interactions. Two types of cations with stronger ionic interactions can be packed in a denser arrangement in mesopores to increase the capacitance, whereas only cations with weaker ionic interactions are allowed to enter micropores without sacrificing the power density. This unique selective charging behavior in different confined porous structure was investigated by solid-state nuclear magnetic resonance experiments and further confirmed theoretically by both density functional theory and molecular dynamics simulations. Our results offer a distinct insight into pairing ionic mixture electrolytes with materials with confined porous characteristics and further propose that it is possible to control the charging process resulting in comprehensive enhancements in SC performance.

Enhancing capacitance of supercapacitor with both organic electrolyte and ionic liquid electrolyte on a biomass-derived carbon

Supercapacitor (SC) with organic electrolyte or ionic liquid (IL) electrolyte can generally store/release higher energy than that with an aqueous electrolyte, due to a larger operating voltage window of a non-aqueous electrolytes. A carbon is synthesized by a facile impregnate-activation method from renewable woody biomass, which has twice of the specific surface area and pore volume than the sample synthesized by conventional KOH activation. Biomass-derived carbons with high ion accessible surface area and highly integrated micropores and mesopores provide superior capacitance, excellent rate capability and good stability in both organic electrolyte and IL electrolytes. Significant enhancement in the capacitance and rate capability were obtained by the generation of micropores similar to the ion size and better pore network through removal of impurities in the biomass. High specific capacitances of 146 F g−1 in the organic electrolyte and 224 F g−1 in the IL electrolyte at current density of 0.1 A g−1 are achieved. Highly integrated micro- and mesoporous structure leads to a good rate capability of 100% capacitance retention at current density up to 10 A g−1 in the organic electrolyte and 67% capacitance retention at current density up to 7 A g−1 in the IL. With the large voltage offered by the non-aqueous electrolyte, the material can store/release high maximum energy of 26 W h kg−1 and 92 W h kg−1 in the organic electrolyte and IL electrolyte, respectively. It reveals that the biomass derived carbon is a promising and cost effective candidate for electrodes in high performance SCs.

Boosted Supercapacitive Energy with High Rate Capability of aCarbon Framework with Hierarchical Pore Structure in an Ionic Liquid

The specific energy of a supercapacitor (SC) with an ionic liquid (IL)-based electrolyte is larger than that using an aqueous electrolyte owing to the wide operating voltage window provided by the IL. However, the wide-scale application of high-energy SCs using ILs is limited owing to a serious reduction of the energy with increasing power. The introduction of macropores to the porous material can mitigate the reduction in the gravimetric capacitance at high rates, but this lowers the volumetric capacitance. Synthetic polymers can be used to obtain macroporous frameworks with high apparent densities, but the preservation of the frameworks during activation is challenging. To simultaneously achieve high gravimetric capacitance, volumetric capacitance, and rate capability, a systematic strategy was used to synthesize a densely knitted carbon framework with a hierarchical pore structure by using a polymer. The energy of the SC using the hierarchically porous carbon was 160 Wh kg-1 and 85 Wh L-1 on an active material base at a power of 100 W kg-1 in an IL electrolyte, and 60 % of the energy was still retained at a power larger than 5000 W kg-1 . To illustrate, a full-packaged SC with the material could store/release energy comparable to a Ni-metal hydride battery (gravimetrically) and one order of magnitude higher than a commercial carbon-based SC (volumetrically), within one minute.

Poly(vinylbenzyl chloride)-based poly(ionic liquids) as membranes for CO2 capture from flue gas

Over the last decade, membrane-based CO2 capture using ionic liquids (ILs) has been demonstrated as a promising technology. However, elaborative synthesis of monomers and long-term instability of IL-based composite membranes have so far limited their industrial relevance. In this paper, novel membranes are introduced for CO2 separation using poly(ionic liquids) (PILs) based on polyvinylbenzyl chloride (PVBC). Three PIL-based membranes were prepared as thin-film composites (TFC) by solvent casting with subsequent sealing. They were tested for the CO2 removal from synthetic flue gas. An ammonium-derivatised PVBC-analogue was prepared as a first PIL-type by polymerisation of an IL monomer, whereas two other PILs, respectively with hydroxyethyl ammonium and pyrrolidinium cations, were obtained using a modification of commercial PVBC. Introduction of bis(trifluoromethylsulfonyl)imide (Tf2N) anions was accomplished by metathesis. A thorough characterisation of the material structure, composition, membrane morphology and gas separation properties demonstrates that the presence of hydroxyl groups in the polycation enhanced the interaction with CO2 molecules. The mixed-gas selectivity increases with the higher positive charge on the cation species (hydroxyethyl-dimethylammonium > trimethylammonium > pyrrolidinium). More importantly, experiments performed in humidified conditions particularly revealed a doubled CO2 permeance and a 20–30% increased selectivity in comparison to dry conditions. These developments are spurring the application of PIL-based TFC membranes for CO2 capture from flue gas streams.

Boosting Properties of 3D Binder-Free Manganese Oxide Anodes by Preformation of a Solid Electrolyte Interphase

Huge irreversible capacity loss prevents the successful use of metal oxide anodes in Li-ion full cells. Here, we focus on the critical prelithiation step and demonstrate the challenge of electrolyte decomposition on a pristine anode in a full cell. Both an electrochemical activation process (54 h) with Li metal and a new electrolytic process (75 min) without Li metal were used to preform complete solid electrolyte interphase (SEI) layers on 3 D binder-free MnOy -based anodes. The preformed SEI layers mitigated the electrolyte decomposition effectively and widened the working voltage for the MnOy /LiMn2 O4 full cell, which resulted in a big boost of the specific energy to 300 and 200 W h kgcathode (-1) , largely improved cycling stability, and much higher specific power (4200 W h kgtotal (-1) ) compared to conventional Li-ion batteries. Detailed characterization, such as cyclic voltammetry, scanning transmission electron microscopy, and FTIR spectroscopy, gives mechanistic insight into SEI preformation. This work provides guidance for the design of anode SEI layers and enables the application of oxides for Li-ion battery full cells.