In article number 2007826, Morgan Stefik and co‐workers determine unambiguous nanostructure‐property relationships using a series of nanoscale T‐Nb2O5 architectures that vary by a single spatial variable at a time by using persistent micelle templates. The departure of lithiation behavior from intercalation pseudocapacitance with surface‐limited kinetics depend sensitively upon the architecture's intercalation length scale. Identifying such nanostructure–performance relationships enables tailored architecture designs that are “nano‐optimized” to specific needs.
Intercalation pseudocapacitance has emerged as a promising energy storage mechanism that combines the energy density of intercalation materials with the power density of capacitors. Niobium pentoxide was the first material described as exhibiting intercalation pseudocapacitance. The electrochemical kinetics for charging/discharging this material are surface‐limited for a wide range of conditions despite intercalation via diffusion. Investigations of niobium pentoxide nanostructures are diverse and numerous; however, none have yet compared performance while adjusting a single architectural parameter at a time. Such a comparative approach reduces the reliance on models and the associated assumptions when seeking nanostructure–property relationships. Here, a tailored isomorphic series of niobium pentoxide nanostructures with constant pore size and precision tailored wall thickness is examined. The sweep rate at which niobium pentoxide transitions from being surface‐limited to being diffusion‐limited is shown to depend sensitively upon the nanoscale dimensions of the niobium pentoxide architecture. Subsequent experiments probing the independent effects of electrolyte concentration and film thickness unambiguously identify solid‐state lithium diffusion as the dominant diffusion constraint even in samples with just 48.5–67.0 nm thick walls. The resulting architectural dependencies from this type of investigation are critical to enable energy‐dense nanostructures that are tailored to deliver a specific power density.
Mesoporous microparticles are an
attractive platform to deploy
high-surface-area nanomaterials in a convenient particulate form that
is broadly compatible with diverse device manufacturing methods. The
applications for mesoporous microparticles are numerous, spanning
the gamut from drug delivery to catalysis and energy storage. For
most applications, the performance of the resulting materials depends
upon the architectural dimensions including the mesopore size, wall
thickness, and microparticle size, yet a synthetic method to control
all these parameters has remained elusive. Furthermore, some mesoporous
microparticle reports noted a surface skin layer which has not been
tuned before despite the important effect of such a skin layer upon
transport/encapsulation. In the present study, material precursors
and block polymer micelles are combined to yield mesoporous materials
in a microparticle format due to phase separation from a homopolymer
matrix. The skin layer thickness was kinetically controlled where
a layer integration via diffusion (LID) model explains its production
and dissipation. Furthermore, the independent tuning of pore size
and wall thickness for mesoporous microparticles is shown for the
first time using persistent micelle templates (PMT). Last, the kinetic
effects of numerous processing parameters upon the microparticle size
are shown.
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