950 research outputs found

    A zero dimensional model of lithium-sulfur batteries during charge and discharge

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    Lithium-sulfur cells present an attractive alternative to Li-ion batteries due to their large energy density, safety, and possible low cost. Their successful commercialisation is dependent on improving their performance, but also on acquiring sufficient understanding of the underlying mechanisms to allow for the development of predictive models for operational cells. To address the latter, we present a zero dimensional model that predicts many observed features in the behaviour of a lithium-sulfur cell during charge and discharge. The model accounts for two electrochemical reactions via the Nernst formulation, power limitations through Butler-Volmer kinetics, and precipitation/dissolution of one species, including nucleation. It is shown that the precipitation/dissolution causes the flat shape of the low voltage plateau, typical of the lithium-sulfur cell discharge. During charge, it is predicted that the dissolution can act as a bottleneck, as for large enough currents smaller amounts dissolve. This results in reduced charge capacity and an earlier onset of the high plateau reaction, such that the two plateaus merge. By including these effects, the model improves on the existing zero dimensional models, while requiring considerably fewer input parameters and computational resources. The model also predicts that, due to precipitation, the customary way of experimentally measuring the open circuit voltage from a low rate discharge might not be suitable for lithium-sulfur. This model can provide the basis for mechanistic studies, identification of dominant effects in a real cell, predictions of operational behaviour under realistic loads, and control algorithms for applications

    Environmental impact of hybrid and electric vehicles

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    Hybrid and electric vehicles play a critical role in reducing global greenhouse gas emissions, with transport estimated to contribute to 14% of the 49 GtCO2eq produced annually. Analysis of only the conversion efficiency of powertrain technologies can be misleading, with pure battery electric and hybrid vehicles reporting average efficiencies of 92% and 35% in comparison with 21% for internal combustion engine vehicles. A fairer comparison would be to consider the well-to-wheel efficiency, which reduces the numbers to 21–67%, 25% and 12%, respectively. The large variation in well-to-wheel efficiency of pure battery electric vehicles highlights the importance of renewable energy generation in order to achieve true environmental benefits. When calculating the energy return on investment of the various technologies based on the current energy generation mix, hybrid vehicles show the greatest environmental benefits, although this would change if electricity was made with high amounts of renewables. In an extreme scenario with heavy coal generation, the CO2eq return on investment can actually be negative for pure electric vehicles, highlighting the importance of renewable energy generation further. The energy impact of production is generally small (∼6% of lifetime energy) and, similarly, recycling is of a comparable magnitude, but it is less well studied

    Additive manufacturing for solid oxide cell electrode fabrication

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    © The Electrochemical Society.Additive manufacturing can potentially offer a highly-defined electrode microstructure, as well as fast and reproducible electrode fabrication. Selective laser sintering is an additive manufacturing technique in which three-dimensional structures are created by bonding subsequent layers of powder using a laser. Although selective laser sintering can be applied to a wide range of materials, including metals and ceramics, the scientific and technical aspects of the manufacturing parameters and their impact on microstructural evolution during the process are not well understood. In the present study, a novel approach for electrode fabrication using selective laser sintering was evaluated by conducting a proof of concept study. A Ni-patterned fuel electrode was laser sintered on an yttria-stabilized zirconia substrate. The optimization process of laser parameters (laser sintering rate and laser power) and the electrochemical results of a full cell with a laser sintered electrode are presented. The challenges and prospects of using selective laser sintering for solid oxide cell fabrication are discussed

    Opportunities for disruptive advances through engineering for next generation energy storage

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    Throughout human history, major economic disruption has been due to technological breakthroughs. Since 1990 the energy density of lithium-ion cells has increased by a factor of four and the cost has dropped by a factor of 10. This has caused disruption to the energy industry, but advances are slowing. The manufacturing and supply chain complexity means that the next big technology will take 15 years to dominate. The academic literature charts this process of development and can be used to show what is in the pipeline. Three candidates that have had a large increase in publication count are: lithium sulphur, solid-state, and sodium-ion technology. From the level of investments in start-ups and academic publication counts, solid‑state cells are closest to maturity. To identify disruption potential, look at uncertainty in performance. Cell lifetime in lithium-ion cells indicates room for improvement. Define a new disruption metric: . Look for areas of industry that lower this metric. Thermal management is a lucrative area for improvement. Cooling the cell tabs of a 5Ah cell reduces the lifetime cost by 66%, compared to 8%/pa for 13 years relying on cost reduction. Second life applications lower the lifetime cost by using the remaining 75% of energy throughput available in a cell after use in an electric vehicle. Drop-in changes to standard manufacturing processes enable huge disruption. Electrolyte additives can increase cell life by 10 times, lowering lifetime cost by 90% in a simple manufacturing intervention

    The Effect of Salt and Pyrophosphate on the Structure of Meat

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    Our obective was to determine whether or not salt and pyrophosphate have the same effect on the structure of pieces of meat as they have on isolated myofibrils. Blocks of pig M. longissimus dorsi were incubated in solutions of sodium chloride at pH 5.5 or sodium chloride plus sodium pyrophosphate at pH 5.5 or 8.0. The blocks were obtained from fresh (24h post- mortem) or aged (72h post-mor tem) muscle and incubated for 5 or 24h with minimal agitation. There was considerable uptake of water by the tissue especially at the higher pH and longer times. Electron microscopy of the meat incubated in salt plus pyrophosphate at pH 8.0 revealed complete or nearly complete extraction of the A-band to a depth of at least one fibre from the surface. In meat incubated in salt plus pyrophosphate at pH 5.5 the extraction of the A-band was 1 ess complete and appeared to occur only near the surface. In salt alone no extraction of the A-band occurred. Swelling of myofibrils close to the surface could be detected either by a reduction of density or by greater separation of filaments . Break-up of the Z-line, probably due to mechanical disruption imposed by swelling of myofibrils, was a common feature of the salt treatments. Mitochondria near the surface were grossly swollen, especially with salt plus pyrophosphate at pH 8.0 At low pH amorphous material was observed inside and outside the cell membrane, but at high pH filamentous material was present in these areas

    Insights into the role of silicon and graphite in the electrochemical performance of silicon/graphite blended electrodes with a multi-material porous electrode model

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    Silicon/graphite blended electrodes are promising candidates to replace graphite in lithium ion batteries, benefiting from the high capacity of silicon and the good structural stability of carbon. Models have proven essential to understand and optimise batteries with new materials. However, most previous models treat silicon/graphite blends as a single “lumped” material, offering limited understanding of the behaviors of the individual materials and thus limited design capability. Here, we present a multi-material model for silicon/graphite electrodes with detailed descriptions of the contributions of the individual active materials. The model shows that silicon introduces voltage hysteresis to silicon/graphite electrodes and consequently a “plateau shift” during delithiation of the electrodes. There will also be competition between the silicon and graphite lithiation reactions depending on silicon/graphite ratio. A dimensionless competing factor is derived to quantify the competition between the two active materials. This is demonstrated to be a useful indicator for active operating regions for each material and we demonstrate how it can be used to design cycling protocols for mitigating electrode degradation. The multi-material electrode model can be readily implemented into full-cell models and coupled with other physics to guide further development of lithium ion batteries with silicon-based electrodes

    Regularized MPC for power management of hybrid energy storage systems with applications in electric vehicles

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    This paper examines the application of Regularized Model Predictive Control (RMPC) for Power Management (PM) of Hybrid Energy Storage Systems (HESSs). To illustrate, we apply the idea to the PM problem of a battery-supercapacitors (SCs) powertrain to reduce battery degradation in Electric Vehicles (EVs). While the application of Quadratic MPC (QMPC) in PM of HESS is not new, the idea to examine RMPC here is motivated by its capabilities to prioritize actuator actions and efficiently allocate control effort, as advocated by recent works in the control and MPC literature. Thorough simulations have been run over standard urban test drive cycles. It is found out that QMPC and RMPC, compared to rule-based PM strategies, could reduce the battery degradation over 70%. It is also shown that RMPC can slightly outperform QMPC in reducing battery degradation. Moreover, RMPC, compared to QMPC, could potentially extend the range of that SCs can be used, thus exploiting the degree of freedom of the powertrain to a larger extent. We also make some discussions on the feasibility issues and tuning challenges that RMPC faces, among others

    Force generation examined by laser temperature-jumps in shortening and lengthening mammalian (rabbit psoas) muscle fibres

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    We examined the tension change induced by a rapid temperature jump (T-jump) in shortening and lengthening active muscle fibres. Experiments were done on segments of permeabilized single fibres (length (L0) ∼2 mm, sarcomere length 2.5 μm) from rabbit psoas muscle; [MgATP] was 4.6 mm, pH 7.1, ionic strength 200 mm and temperature ∼9°C. A fibre was maximally Ca2+-activated in the isometric state and a ∼3°C, rapid (< 0.2 ms), laser T-jump applied when the tension was approximately steady in the isometric state, or during ramp shortening or ramp lengthening at a limited range of velocities (0–0.2 L0 s−1). The tension increased to 2- to 3 × P0 (isometric force) during ramp lengthening at velocities > 0.05 L0 s−1, whereas the tension decreased to about < 0.5 × P0 during shortening at 0.1–0.2 L0 s−1; the unloaded shortening velocity was ∼1 L0 s−1 and the curvature of the force–shortening velocity relation was high (a/P0 ratio from Hill's equation of ∼0.05). In isometric state, a T-jump induced a tension rise of 15–20% to a new steady state; by curve fitting, the tension rise could be resolved into a fast (phase 2b, 40–50 s−1) and a slow (phase 3, 5–10 s−1) exponential component (as previously reported). During steady lengthening, a T-jump induced a small instantaneous drop in tension, followed by recovery, so that the final tension recorded with and without a T-jump was not significantly different; thus, a T-jump did not lead to a net increase of tension. During steady shortening, the T-jump induced a pronounced tension rise and both its amplitude and the rate (from a single exponential fit) increased with shortening velocity; at 0.1–0.2 L0 s−1, the extent of fibre shortening during the T-jump tension rise was estimated to be ∼1.2% L0 and it was shorter at lower velocities. At a given shortening velocity and over the temperature range of 8–30°C, the rate of T-jump tension rise increased with warming (Q10 ≈ 2.7), similar to phase 2b (endothermic force generation) in isometric muscle. Results are discussed in relation to the previous findings in isometric muscle fibres which showed that a T-jump promotes an early step in the crossbridge–ATPase cycle that generates force. In general, the finding that the T-jump effect on active muscle tension is pronounced during shortening, but is depressed/inhibited during lengthening, is consistent with the expectations from the Fenn effect that energy liberation (and acto-myosin ATPase rate) in muscle are increased during shortening and depressed/inhibited during lengthening

    Strain induced electrochemical behaviors of ionic liquid electrolytes in an electrochemical double layer capacitor: Insights from molecular dynamics simulations.

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    Electrochemical Double Layer Capacitors (EDLCs) with ionic liquid electrolytes outperform conventional ones using aqueous and organic electrolytes in energy density and safety. However, understanding the electrochemical behaviors of ionic liquid electrolytes under compressive/tensile strain is essential for the design of flexible EDLCs as well as normal EDLCs, which are subject to external forces during assembly. Despite many experimental studies, the compression/stretching effects on the performance of ionic liquid EDLCs remain inconclusive and controversial. In addition, there is hardly any evidence of prior theoretical work done in this area, which makes the literature on this topic scarce. Herein, for the first time, we developed an atomistic model to study the processes underlying the electrochemical behaviors of ionic liquids in an EDLC under strain. Constant potential non-equilibrium molecular dynamics simulations are conducted for EMIM BF4 placed between two graphene walls as electrodes. Compared to zero strain, low compression of the EDLC resulted in compromised performance as the electrode charge density dropped by 29%, and the performance reduction deteriorated significantly with a further increase in compression. In contrast, stretching is found to enhance the performance by increasing the charge storage in the electrodes by 7%. The performance changes with compression and stretching are due to changes in the double-layer structure. In addition, an increase in the value of the applied potential during the application of strain leads to capacity retention with compression revealed by the newly performed simulations. [Abstract copyright: © 2023 Author(s). Published under an exclusive license by AIP Publishing.

    Irreversible vs reversible capacity fade of lithium-sulfur batteries during cycling: the effects of precipitation and shuttle

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    Lithium-sulfur batteries could deliver significantly higher gravimetric energy density and lower cost than Li-ion batteries. Their mass adoption, however, depends on many factors, not least on attaining a predictive understanding of the mechanisms that determine their performance under realistic operational conditions, such as partial charge/discharge cycles. This work addresses a lack of such understanding by studying experimentally and theoretically the response to partial cycling. A lithium-sulfur model is used to analyze the mechanisms dictating the experimentally observed response to partial cycling. The zero-dimensional electrochemical model tracks the time evolution of sulfur species, accounting for two electrochemical reactions, one precipitation/dissolution reaction with nucleation, and shuttle, allowing direct access to the true cell state of charge. The experimentally observed voltage drift is predicted by the model as a result of the interplay between shuttle and the dissolution bottleneck. Other features are shown to be caused by capacity fade. We propose a model of irreversible sulfur loss associated with shuttle, such as caused by reactions on the anode. We find a reversible and an irreversible contribution to the observed capacity fade, and verify experimentally that the reversible component, caused by the dissolution bottleneck, can be recovered through slow charging. This model can be the basis for cycling parameters optimization, or for identifying degradation mechanisms relevant in applications. The model code is released as Supplementary material B
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