A minimal-architecture zinc–bromine battery that eliminates expensive balance-of-plant components is demonstrated with stable performance and low cost.
In this work we build upon acoustic-electrochemical correlations to investigate the relationships between sound wave structure and chemo-mechanical properties of a pouch cell battery. Cell thickness imaging and wave detection...
Fast-charging
lithium-ion batteries in 15 min or less is an important
capability that may lead to greater electric vehicle adoption but
remains challenging to implement. Heating to moderate temperature
(40–50 °C) during the fast-charge step has been introduced
as one method to mitigate the loss of lithium inventory by enhancing
transport and kinetics. Unfortunately, this edge has two sides as
even moderate temperature elevation will accelerate capacity fade
due to interface and electrolyte degradation. While the thermal enhancement
of transport and degradation is intuitive, the mechanistic effects
of various temperature ranges on fast-charging capabilities are under-reported.
The present work examines the balance between aging, temperature,
and charge rate and describes cycling protocols in combination with
high-temperature ranges that may enable fast-charging capabilities.
A galvanostatic intermittent titration technique (GITT) analysis reveals
non-Arrhenius diffusion behavior at the cell level. This shift is
attributed to a mechanistic difference in graphite staging at temperatures
above and below 40 °C. Coupled with differential capacity and
voltage analysis, we indicate the specific phase transition that is
kinetically sluggish at low temperatures relative to the other phase
transitions but is comparable to the other phase transitions at high
temperatures. This reduction of the transport bottleneck, in addition
to the benefits of thermal activation of diffusion, further minimizes
the likelihood of lithium plating that is triggered by particle scale
transport challenges well before full lithiation of the graphite.
This helps to explain recently described outsized successes of elevated
temperature fast-charge protocols, but also questions the temperature
at which fast-charge should take place, as the diffusivity gains for
55 vs 45 °C are less dramatic than 45 vs 35 °C, and side
reactions may deter operation above 50 °C. These diffusivity
studies are connected with long-term aging studies which indicate
improved high-temperature aging at lower states-of-charge rather than
higher states-of-charge. Taken together, we introduce a cycling protocol
utilizing a constant current fast-charge at high temperature to take
advantage of lower overpotentials, shorter duration at high states-of-charge,
and improved cell diffusivity.
Natural convection arises in many types of fluid flow where a diffusive species causes a density change to the fluid. Electrochemical reactions are typically strong drivers of this flow given the combination of a large density change due to reaction and a relatively slow rate of species diffusion. Density stratification in lead-acid batteries is a well documented phenomenon, but the effect of density driven flow is not typically investigated in many electrochemical systems where it is a surprisingly important transport mode. Experiments and models show that a zinc-bromine cell's performance is dominated by this natural convection effect and results in a much higher utilization than would be expected based solely on a diffusive model. Finally we show how electrolyte composition can substantially modify the properties of this flow and how this can potentially benefit other systems.
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