Prussian Blue Analogue (PBA)-Zn aqueous batteries are attractive because of the high potential of PBA against Zn (~1.7 V), relative safety of the system, and high rate capability. But, despite the long cycle life of PBA half-cells, full PBA-Zn battery systems studied thus far have typically reported only up to 100 cycles and suffer significant capacity fade beyond that. In this work we demonstrate that the loss in capacity retention and cycle life is a combined effect of Zn 2+ ion poisoning at the PBA cathode, as well as dendrite formation in the zinc anode. We address both these issues via the use of a dual ion (Na + as the primary charge carrier) electrolyte and hyper-dendritic Zinc (HD Zn) as the anode. The copper hexacyanoferrate (CuHcf) vs. HD Zn system with Na + ion electrolyte demonstrated herein exhibits 90% (83%) capacity retention after 300 (500) cycles at a 5C rate and a 3% reduction in usable capacity from 1C to 5C. Detailed characterization is done using in situ synchrotron energy-dispersive XRD (EDXRD), conventional XRD, XPS, SEM, TEM, and electrochemical techniques.
Ultrasonic analysis was used to predict the state of charge and state of health of lithium-ion pouch cells that have been cycled for several hundred cycles. The repeatable ultrasonic trends are reduced to two key metrics: time of flight shift and total signal amplitude, which are then used with voltage data in a supervised machine learning technique to build a model for state of charge (SOC) prediction. Using this model, cell SOC is predicted to ∼1% accuracy for both lithium cobalt oxide and lithium iron phosphate cells. Elastic wave propagation theory is used to explain that the changes in ultrasonic signal are related to changes in the material properties of the active materials (i.e., elastic modulus and density) during cycling. Finally, we show the machine learning model can accurately predict cell state of health with an error ∼1%. This is accomplished by extending the data inputs into the model to include full ultrasonic waveforms at top of charge. A key component of an electric vehicle is the battery management system (BMS), which is responsible for controlling the operating conditions on a given battery cell (or stack of cells) in order to optimize the performance and lifetime of the full battery system. The most effective battery management systems must be able to track battery state of charge (SOC), state of health (SOH) and cell failure, including early prediction of catastrophic failure. Despite the importance of this task, being able to reliably determine SOC, SOH and failure at low cost still presents a significant challenge. A range of methods exist at present, however the simplest methods can prove inaccurate, and more complex methods are not suitable for low-cost, in-operando SOC determination. 1-3For instance, in its most common implementation, SOC prediction consists of voltage monitoring (direct measurement) combined with coulomb-counting (book-keeping).1 This can present challenges for a variety of reasons. First, for voltage measurements, the flatness of voltage readings over the majority of battery capacity, especially for lithium iron phosphate (LFP) cells, presents difficulties. 4 Furthermore, voltage fade, changing cell impedances, and varying discharge rates impact measured voltage, obscuring true SOC. Second, coulomb counting is also an inexact science, as discharge rate, environmental factors such as temperature, and cell degradation can all impact the actual capacity for any given discharge. This can lead to a cycle of abuse, whereby discharge conditions lead to an incorrect estimate of SOC, and therefore the cell becomes inadvertently over-discharged. This causes damage to the cell, which leads to further inaccuracy in the SOC prediction, resulting in continued over-discharging and cell damage. Effectively, a battery "death-spiral" ensues.One method to further increase the accuracy of battery management systems is to introduce a technique that can directly measure the physical state of the battery to enhance the determination of SOC, SOH, and cell failure, especially when applied i...
A minimal-architecture zinc–bromine battery that eliminates expensive balance-of-plant components is demonstrated with stable performance and low cost.
Stable long-term cycling and solid-electrolyte-interphase (SEI) formation are key challenges in the design of Si/graphite composites as Li-ion battery (LIB) anode materials. Typically, these long-term cycling properties are examined in flooded half-cell settings making use of a Li-metal counter electrode and a Si/graphite working electrode. This form factor has the advantage of offering an unlimited supply of Li-ions and electrolyte, thus isolating performance degradation to the passivation of the working electrode. However, half-cell studies are ineffective in revealing performance and degradation mechanisms of the Si/graphite composite in a more commercially realistic full cell setting. This paper outlines an operando acoustic technique that can offer insights on SEI formation and capacity degradation of Si/graphite composites in a full cell setting. Through a combination of electrochemical and chemical analyses, we show that increasing passivation of the silicon particles in the Si/graphite composite anode is correlated with an increase in the acoustic time-of-flight shift. We further show that temporary loss of the acoustic signal during the first cycle is associated with significant gassing of the cell. The operando acoustic technique outlined here is low-cost, simple to setup and has the potential for localized resolution, indicating usefulness in commercial-scale Si/graphite cell quality control and diagnosis.
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