Tuning
crystallinity and surface functionality are supreme for
extracting maximum charge storage efficiency from electrode materials
for energy storage devices. Contextually, suitable organic additives
with sluggish precipitants are known to significantly regulate the
kinetics of reactions and dimensionality of crystals leading to structures
with tuned crystallinity and surface functionality. Accordingly, herein,
extremely uniform sedgelike highly porous Co3O4 nanoarrays were synthesized by homogeneous precipitation method
using sodium dodecyl sulfate as the organic additive and urea as the
sluggish precipitant, under hydrothermal condition. The distinctive
physicochemical properties of Co3O4 were identified
by powder X-ray diffraction, field-emission scanning electron microscopy,
high-resolution transmission electron microscopy, Brunauer–Emmett−Teller
surface area, and UV–vis diffuse reflectance spectroscopy analyses,
which show ∼2 nm crystallinity, uniform sedgelike structure,
presence of model micro- and mesopores, and signatures of quantum
confinement. Thorough electrochemical studies show that the Co3O4 nanoarrays sample possess lower electrochemical
series resistance of 0.4 Ω, and it offers a very high rate-specific
capacitance of 2510 F g–1 at an applied current
density of 4 A g–1, and retains ∼42% of capacitance
at eightfold higher applied current density, when measured in a three-electrode
assembly. The sedgelike Co3O4 was used as a
positive electrode material, and its compatibility was assessed with
microbelt-like two-dimensional (2D) Bi2O3 as
the negative electrode material, in a redox ensuing Co3O4 || Bi2O3 asymmetric supercapacitor
(ASC) device with a wide operating potential window of 1.4 V. The
ASC device offers very high areal and mass-specific capacitance of
479 mF cm–2 & 71 F g–1, respectively,
at an applied current density of 6 mA cm–2 and exhibits
an excellent rate capacitance of ∼50% at an extremely high
current density of 48 mA cm–2. The ASC device also
retains ∼95% of the areal capacitance after 5000 galvanostatic
charge–discharge cycles at an applied current density of 10
mA cm–2. The Co3O4 || Bi2O3 ASC device also offers high energy density of
∼38.5 Wh kg–1 at a power density of ∼1225
W kg–1 and retains ∼47% of the energy density
at a very high power density of ∼9473 W kg–1. Factually, the present study manifests that ideal porosity and
surface properties of sedgelike Co3O4 nanoarrays
allow unimpeded OH– ion diffusion, and the bundled
structure provides flake-off resistance/mechanical stability during
harmonious redox reactions with 2D Bi2O3 during
high rate operation of the ASC device. It is proposed that the all-new
Co3O4 || Bi2O3 asymmetric
assimilation will open new avenues in the designing of high rate ASCs
for power grid applications.