2 research outputs found
Effect of Tin Doping on α-Fe<sub>2</sub>O<sub>3</sub> Photoanodes for Water Splitting
Sputter-deposited films of α-Fe<sub>2</sub>O<sub>3</sub> of
thickness 600 nm were investigated as photoanodes for solar water
splitting and found to have photocurrents as high as 0.8 mA/cm<sup>2</sup> at 1.23 V vs the reversible hydrogen electrode (RHE). Sputter-deposited
films, relative to nanostructured samples produced by hydrothermal
synthesis,, permit facile characterization of the role
and placement of dopants. The Sn dopant concentration in the α-Fe<sub>2</sub>O<sub>3</sub> varies as a function of distance from the fluorine-doped
tin oxide (FTO) interface and was quantified using secondary ion mass
spectrometry (SIMS) to give a mole fraction of cations of approximately
0.02% at the electrolyte interface. Additional techniques for determining
dopant density, including energy dispersive X-ray spectroscopy (EDS),
electron energy loss spectroscopy (EELS), electrochemical impedance
spectroscopy (EIS), and conductivity measurements, are compared and
discussed. Based on this multifaceted data set, we conclude that not
all dopants present in the α-Fe<sub>2</sub>O<sub>3</sub> are
active. Dopant activation, rather than just increasing surface area
or dopant concentration, is critical for improving metal oxide performance
in water splitting. A more complete understanding of dopant activation
will lead to further improvements in the design and response of nanostructured
photoanodes
Electrolyte Stability Determines Scaling Limits for Solid-State 3D Li Ion Batteries
Rechargeable, all-solid-state Li ion batteries (LIBs)
with high
specific capacity and small footprint are highly desirable to power
an emerging class of miniature, autonomous microsystems that operate
without a hardwire for power or communications. A variety of three-dimensional
(3D) LIB architectures that maximize areal energy density has been
proposed to address this need. The success of all of these designs
depends on an ultrathin, conformal electrolyte layer to electrically
isolate the anode and cathode while allowing Li ions to pass through.
However, we find that a substantial reduction in the electrolyte thickness,
into the nanometer regime, can lead to rapid self-discharge of the
battery even when the electrolyte layer is conformal and pinhole free.
We demonstrate this by fabricating individual, solid-state nanowire
core–multishell LIBs (NWLIBs) and cycling these inside a transmission
electron microscope. For nanobatteries with the thinnest electrolyte,
≈110 nm, we observe rapid self-discharge, along with void formation
at the electrode/electrolyte interface, indicating electrical and
chemical breakdown. With electrolyte thickness increased to 180 nm,
the self-discharge rate is reduced substantially, and the NWLIBs maintain
a potential above 2 V for over 2 h. Analysis of the nanobatteries’
electrical characteristics reveals space-charge limited electronic
conduction, which effectively shorts the anode and cathode electrodes
directly through the electrolyte. Our study illustrates that, at these
nanoscale dimensions, the increased electric field can lead to large
electronic current in the electrolyte, effectively shorting the battery.
The scaling of this phenomenon provides useful guidelines for the
future design of 3D LIBs