2 research outputs found
Fabrication of Porous Carbon/TiO<sub>2</sub> Composites through Polymerization-Induced Phase Separation and Use As an Anode for Na-Ion Batteries
Polymerization-induced phase separation
of nanoparticle-filled solution is demonstrated as a simple approach
to control the structure of porous composites. These composites are
subsequently demonstrated as the active component for sodium ion battery
anode. To synthesize the composites, we dissolved/dispersed titanium
oxide (anatase) nanoparticles (for sodium insertion) and polyÂ(hydroxybutyl
methacrylate) (PHBMA, porogen) in furfuryl alcohol (carbon precursor)
containing a photoacid generator (PAG). UV exposure converts the PAG
to a strong acid that catalyzes the furfuryl alcohol polymerization.
This polymerization simultaneously decreases the miscibility of the
PHBMA and reduces the mobility in the mixture to kinetically trap
the phase separation. Carbonization of this polymer composite yields
a porous nanocomposite. This nanocomposite exhibits nearly 3-fold
greater gravimetric capacity in Na-ion batteries than the same titanium
oxide nanoparticles that have been coated with carbon. This improved
performance is attributed to the morphology as the carbon content
in the composite is five times that of the coated nanoparticles. The
porous composite materials exhibit stable cyclic performance. Moreover,
the battery performance using materials from this polymerization-induced
phase separation method is reproducible (capacity within 10% batch-to-batch).
This simple fabrication methodology may be extendable to other systems
and provides a facile route to generate reproducible hierarchical
porous morphology that can be beneficial in energy storage applications
Kinetics of UV Irradiation Induced Chain Scission and Cross-Linking of Coumarin-Containing Polyester Ultrathin Films
Photoresponsive thin films are commonly
encountered as high performance
coatings as well as critical component, photoresists, for microelectronics
manufacture. Despite intensive investigations into the dynamics of
thin glassy polymer films, studies involving reactions of thin films
have typically been limited by difficulties in decoupling segregation
of reacting components or catalysts due to the interfaces. Here, thin
films of coumarin polyesters overcome this limitation where the polyester
undergoes predominately cross-linking upon irradiation at 350 nm,
while chain scission occurs with exposure to 254 nm light. Spectroscopic
ellipsometry is utilized to track these reactions as a function of
exposure time to elucidate the associated reaction kinetics for films
as thin as 15 nm. The cross-linking appears to follow a second order
kinetic rate law, while oxidation of the coumarin that accompanies
the chain scission and enables this reaction to be tracked spectroscopically
appears to be a first order reaction in coumarin concentration. Because
of the asymmetry in the coumarin diol monomer and the associated differences
in local structure that result during formation of the polyester,
two populations of coumarin are required to fit the reaction kinetics;
10–20% of the coumarin is significantly more reactive, but
these groups appear to undergo chain scission/oxidation at both wavelengths.
These reaction rate constants are nearly independent (within 1 order
of magnitude) of film thickness down to 15 nm. There is maximum rate
at a finite thickness for the 254 nm exposure, which we attribute
to constructive interference of the UV radiation within the polymer
film, rather than typical confinement effects; no thickness dependence
in reaction rates is observed for the 350 nm exposure. The utilization
of a single polymer with two distinct reactions enables unambiguous
investigation of thickness effects on reactions