There are an increasing number of studies regarding active electrode materials that undergo faradaic reactions but are used for electrochemical capacitor applications. Unfortunately, some of these materials are described as "pseudocapacitive" materials despite the fact that their electrochemical signature (e.g., cyclic voltammogram and charge/discharge curve) is analogous to that of a "battery" material, as commonly observed for Ni(OH) 2 and cobalt oxides in KOH electrolyte. Conversely, true pseudocapacitive electrode materials such as MnO 2 display electrochemical behavior typical of that observed for a capacitive carbon electrode. The difference between these two classes of materials will be explained, and we demonstrate why it is inappropriate to describe nickel oxide or hydroxide and cobalt oxide/hydroxide as pseudocapacitive electrode materials.
The next generation of high-performance batteries should include alternative chemistries that are inherently safer to operate than nonaqueous lithium-based batteries. Aqueous zinc-based batteries can answer that challenge because monolithic zinc sponge anodes can be cycled in nickel-zinc alkaline cells hundreds to thousands of times without undergoing passivation or macroscale dendrite formation. We demonstrate that the three-dimensional (3D) zinc form-factor elevates the performance of nickel-zinc alkaline cells in three fields of use: (i) >90% theoretical depth of discharge (DOD) in primary (single-use) cells, (ii) >100 high-rate cycles at 40% DOD at lithium-ion-commensurate specific energy, and (iii) the tens of thousands of power-demanding duty cycles required for start-stop microhybrid vehicles.
The design and fabrication of three-dimensional multifunctional architectures from the appropriate nanoscale building blocks, including the strategic use of void space and deliberate disorder as design components, permits a re-examination of devices that produce or store energy as discussed in this critical review. The appropriate electronic, ionic, and electrochemical requirements for such devices may now be assembled into nanoarchitectures on the bench-top through the synthesis of low density, ultraporous nanoarchitectures that meld high surface area for heterogeneous reactions with a continuous, porous network for rapid molecular flux. Such nanoarchitectures amplify the nature of electrified interfaces and challenge the standard ways in which electrochemically active materials are both understood and used for energy storage. An architectural viewpoint provides a powerful metaphor to guide chemists and materials scientists in the design of energy-storing nanoarchitectures that depart from the hegemony of periodicity and order with the promise--and demonstration--of even higher performance (265 references).
The self-limiting reaction of aqueous permanganate with carbon nanofoams produces conformal, nanoscopic deposits of birnessite ribbons and amorphous MnO2 throughout the ultraporous carbon structure. The MnO2 coating contributes additional capacitance to the carbon nanofoam while maintaining the favorable high-rate electrochemical performance inherent to the ultraporous carbon structure of the nanofoam. Such a three-dimensional design exploits the benefits of a nanoscopic MnO2-carbon interface to produce an exceptionally high area-normalized capacitance (1.5 F cm-2), as well as high volumetric capacitance (90 F cm-3).
Pt−Ru is the favored anode catalyst for the oxidation of methanol in direct methanol fuel cells (DMFCs).
The nanoscale Pt−Ru blacks are accepted to be bimetallic alloys as based on their X-ray diffraction patterns.
Our bulk and surface analyses show that although practical Pt−Ru blacks have diffraction patterns consistent
with an alloy assignment, they are primarily a mix of Pt metal and Ru oxides plus some Pt oxides and
only small amounts of Ru metal. Thermogravimetric analysis and X-ray photoelectron spectroscopy of
as-received Pt−Ru electrocatalysts indicate that DMFC materials contain substantial amounts of hydrous
ruthenium oxide (RuO
x
H
y
). A potential misidentification of nanoscale Pt−Ru blacks arises because RuO
x
H
y
is amorphous and cannot be discerned by X-ray diffraction. Hydrous ruthenium oxide is a mixed proton
and electron conductor and innately expresses Ru−OH speciation. These properties are of key importance
in the mechanism of methanol oxidation, in particular, Ru−OH is a critical component of the bifunctional
mechanism proposed for direct methanol oxidation in that it is the oxygen-transfer species that oxidatively
dissociates −C⋮O fragments from the Pt surface. The catalysts and membrane-electrode assemblies of
DMFCs should not be processed at or exposed to temperatures >150 °C, as such conditions deleteriously
lower the proton conductivity of hydrous ruthenium oxide and thus affect the ability of the Ru component
of the electrocatalyst to dissociate water. With this analytical understanding of the true nature of practical
nanoscale Pt−Ru electrocatalysts, we can now recommend that hydrous ruthenium oxide, rather than Ru
metal or anhydrous RuO2, is the preferred Ru speciation in these catalysts.
Contrary to the current understanding of Pt−Ru electrocatalyzed oxidation of methanol, the bimetallic alloy
is not the most desired form of the catalyst. In the nanoscale Pt−Ru blacks used to electrooxidize methanol
in direct methanol fuel cells, Pt0Ru0 has orders of magnitude less activity for methanol oxidation than does
a mixed-phase electrocatalyst containing Pt metal and hydrous ruthenium oxides (RuO
x
H
y
). Bulk, rather than
near-surface, quantities of electron−proton conducting RuO
x
H
y
are required to achieve high activity for
methanol oxidation. The active catalyst forms a nanoscopic, phase-separated hydrons oxide-on-metal structure
that retains the Pt metal−RuO
x
H
y
boundaries required to oxidize methanol fully to carbon dioxide and water.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.