True Performance Metrics in Electrochemical Energy Storage

A dramatic expansion of research in the area of electrochemical energy storage (EES) during the past decade has been driven by the demand for EES in handheld electronic devices, transportation, and storage of renewable energy for the power grid (1–3). However, the outstanding properties reported for new electrode materials may not necessarily be applicable to performance of electrochemical capacitors (ECs). These devices, also called supercapacitors or ultra-capacitors (4), store charge with ions from solution at charged porous electrodes. Unlike batteries, which store large amounts of energy but deliver it slowly, ECs can deliver energy faster (develop high power), but only for a short time. However, recent work has claimed energy densities for ECs approaching (5) or even exceeding that of batteries. We show that even when some metrics seem to support these claims, actual device performance may be rather mediocre. We will focus here on ECs, but these considerations also apply to lithium (Li)—ion batteries

Evaluation of Constant Potential Method in Simulating Electric Double-Layer Capacitors

A major challenge in the molecular simulation of electric double layer capacitors (EDLCs) is the choice of an appropriate model for the electrode. Typically, in such simulations the electrode surface is modeled using a uniform fixed charge on each of the electrode atoms, which ignores the electrode response to local charge fluctuations induced by charge fluctuations in the electrolyte. In this work, we evaluate and compare this Fixed Charge Method (FCM) with the more realistic Constant Potential Method (CPM), [Reed, et al., J. Chem. Phys., 126, 084704 (2007)], in which the electrode charges fluctuate in order to maintain constant electric potential in each electrode. For this comparison, we utilize a simplified LiClO$_4$-acetonitrile/graphite EDLC. At low potential difference ($\Delta\Psi\le 2V$), the two methods yield essentially identical results for ion and solvent density profiles; however, significant differences appear at higher $\Delta\Psi$. At $\Delta\Psi\ge 4V$, the CPM ion density profiles show significant enhancement (over FCM) of "partially electrode solvated" Li$^+$ ions very close to the electrode surface. The ability of the CPM electrode to respond to local charge fluctuations in the electrolyte is seen to significantly lower the energy (and barrier) for the approach of Li$^+$ ions to the electrode surface.Comment: Corrected typo

New Materials and New Configurations for Advanced Electrochemical Capacitors

Today, electrochemical capacitors (ECs) have the potential to emerge as a promising energy storage technology. The weakness of EC systems is certainly the limited energy density, which restricts applications to power delivery over only few seconds. As a consequence, many research efforts are focused on designing new materials to improve energy and power densities. These are reviewed below

TiO2/MoO2 nanocomposite as anode materials for high power Li-ion batteries with exceptional capacity

Nanoparticles of molybdenum(IV) oxide (MoO 2 ) and a TiO 2 /MoO 2 nanocomposite were synthesised via a continuous hydrothermal synthesis process. Both powders were analysed using XRD, XPS, TEM, and BET and evaluated as active materials in anodes for Li-ion half-cells. Cyclic voltammetry and galvanostatic charge/discharge measurements were carried out in the potential window of 0.1 to 3.0 V vs. Li/Li+. Specific capacities of ca. 350 mAh g -1 were obtained for both materials at low specific currents (0.1 A g -1 ); TiO 2 /MoO 2 composite electrodes showed superior rate behaviour & stability under cycling (compared to MoO 2 ), with stable specific capacities of ca. 265 mAh g -1 at a specific current of 0.5 A g -1 and ca. 150 mAh g -1 after 350 cycles at a specific current of 2.5 A g -1 . The improved performance of the composite material, compared to MoO 2 , was attributed to a smaller particle size, improved stability to volume changes (during cycling), and lower charge transfer resistance during cycling. Li-ion hybrid electrochemical capacitors using TiO 2 /MoO 2 composite anodes and activated carbon (AC) cathodes were evaluated and showed excellent performance with an energy density of 44 Wh kg -1 at a power density of 600 W kg -1

Ion-liquid based super-capacitors with inner gate diode-like separators

We demonstrate that the capacitance of ionic-liquid filled supercapacitors is substantially increased by placing a diode-like structure on the separator membrane. We call the structured separator: gate, and demonstrate that the order of a p-n layout with respect to the auxiliary electrode affects the overall cell's capacitance. The smallest ESR and the largest capacitance values are noted when the p-side is facing the auxiliary electrode.Comment: 11 pages, 8 figure