Batteries and Supercapacitors
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Journal articleLiu X, Taiwo O, Yin C, et al., 2019,
Ionogels are a new class of promising materials for use in all‐solid‐state energy storage devices in which they can function as an integrated separator and electrolyte. However, their performance is limited by the presence of a crosslinking polymer, which is needed to improve the mechanical properties, but compromises their ionic conductivity. Here, directional freezing is used followed by a solvent replacement method to prepare aligned nanocomposite ionogels which exhibit enhanced ionic conductivity, good mechanical strength, and thermal stability simultaneously. The aligned ionogel based supercapacitor achieves a 29% higher specific capacitance (176 F g−1 at 25 °C and 1 A g−1) than an equivalent nonaligned form. Notably, this thermally stable aligned ionogel has a high ionic conductivity of 22.1 mS cm−1 and achieves a high specific capacitance of 167 F g−1 at 10 A g−1 and 200 °C. Furthermore, the diffusion simulations conducted on 3D reconstructed tomography images are employed to explain the improved conductivity in the relevant direction of the aligned structure compared to the nonaligned. This work demonstrates the synthesis, analysis, and use of aligned ionogels as supercapacitor separators and electrolytes, representing a promising direction for the development of wearable electronics coupled with image based process and simulations.
Journal articleCampbell ID, Marzook M, Marinescu M, et al., 2019,
How observable Is lithium plating? Differential voltage analysis to identify and quantify lithium plating following fast charging of cold lithium-Ion batteries, Journal of The Electrochemical Society, Vol: 166, Pages: A725-A739, ISSN: 0013-4651
Fast charging of batteries is currently limited, particularly at low temperatures, due to difficulties in understanding lithium plating. Accurate, online quantification of lithium plating increases safety, enables charging at speeds closer to the electrochemical limit and accelerates charge profile development. This work uses different cell cooling strategies to expose how voltage plateaus arising from cell self-heating and concentration gradients during fast charging can falsely indicate plating, contrary to prevalent current assumptions. A solution is provided using Differential Voltage (DV) analysis, which confirms that lithium stripping is observable. However, scanning electron microscopy and energy-dispersive X-ray analysis are used to demonstrate the inability of the plateau technique to detect plating under certain conditions. The work highlights error in conventional plating quantification that leads to the dangerous underestimation of plated amounts. A novel method of using voltage plateau end-point gradients is proposed to extend the sensitivity of the technique, enabling measurement of lower levels of lithium stripping and plating. The results are especially relevant to automotive OEMs and engineers wishing to expand their online and offline tools for fast charging algorithm development, charge management and state-of-health diagnostics.
Journal articleSong W, Liu X, Wu B, et al., 2019,
Sn@C evolution from yolk-shell to core-shell in carbon nanofibers with suppressed degradation of lithium storage, Energy Storage Materials, Vol: 18, Pages: 229-237, ISSN: 2405-8297
Metallic Sn has high conductivity and high theoretical capacity for lithium storage but it suffers from severe volume change in lithiation/delithiation leading to capacity fade. Yolk-shell and core-shell Sn@C spheres interconnected by carbon nanofibers were synthesized by thermal vapor and thermal melting of electrospun nanofibers to improve the cycling stability. Sn particles in yolk-shell spheres undergo dynamic structure evolution during thermal melting to form core-shell spheres. The core-shell spheres linked along the carbon nanofibers show outstanding performance and are better than the yolk-shell system for lithium storage, with a high capacity retention of 91.8% after 1000 cycles at 1 A g-1. The superior structure of core-shell spheres interconnected by carbon nanofibers has facile electron conductivity and short lithium ion diffusion pathways through the carbon nanofibers and shells, and re-develops Sn@C structures with Sn clusters embedded into carbon matrix during electrochemical cycling, enabling the high performance.
Journal articleDeshagani S, Liu X, Wu B, et al., 2019,
Nickel cobaltite@Poly(3,4-ethylenedioxypyrrole) and carbon nanofiber interlayer based flexible supercapacitor, Nanoscale, Vol: 11, Pages: 2742-2756, ISSN: 2040-3364
Binder free flexible symmetric supercapacitors are developed with nickel cobaltite micro-flowers coated poly(3,4-ethylenedioxypyrrole) (NiCo2O4@PEDOP) hybrid electrodes. Free standing films of carbon nano-fibers (CNF), synthesized by electrospinning, were sandwiched between the NiCo2O4@PEDOP hybrid and the electrolyte coated separators on both sides of the cells. The CNF film conducts both ions and electrons, and confines the charge at the respective electrodes, to result in an improved specific capacitance (SC) and energy density compared to the analogous cell without the CNF interlayers. High SC of 1,775 F g-1 at a low current density of 0.96 A g-1 and a SC of 634 F g-1 achieved at a high current density of 38 A g-1 coupled with a SC retention of ~95% after 5,000 charge-discharge cycles in the NCO@PEDOP/CNF based symmetric supercapacitor, are performance attributes superior to that achieved with NCO and NCO/CNF based symmetric cells. The PEDOP coating serves as a highly conductive matrix for the NCO micro-flowers and also undergoes doping/de-doping during charge-discharge, thus amplifying the overall supercapacitor response, compared to the individual components. The CNF interlayers show reasonably high ion-diffusion coefficients for K+ and OH- propagation implying facile pathways available for movement of ions across the cross-section of the cell, and they also serve as ion reservoirs. The electrode morphologies remain unaffected by cycling, in the presence of the CNF interlayer. LED illumination and a largely unaltered charge storage response was achieved in a mutli-cell configuration, proving the potential for this approach in practical applications.
Journal articleYufit V, Tariq F, Biton M, et al., 2019,
Operando visualisation and multi-scale tomography studies of dendrite formation and dissolution in zinc batteries, Joule, Vol: 3, Pages: 485-502, ISSN: 2542-4351
Alternative battery technologies are required to meet growing energy demands and address the limitations of present technologies. As such, it is necessary to look beyond lithium-ion batteries. Zinc batteries enable high power density while being sourced from ubiquitous and cost-effective materials. This paper presents, for the first time known to the authors, multi-length scale tomography studies of failure mechanisms in zinc batteries with and without commercial microporous separators. In both cases, dendrites were grown, dissolved, and regrown, critically resulting in different morphology of dendritic layer formed on both the electrode and the separator. The growth of dendrites and their volume-specific areas were quantified using tomography and radiography data in unprecedented resolution. High-resolution ex situ analysis was employed to characterize single dendrites and dendritic deposits inside the separator. The findings provide unique insights into mechanisms of metal-battery failure effected by growing dendrites.
Journal articleZhao Y, Spingler FB, Patel Y, et al., 2019,
Localized swelling inhomogeneity detection in lithium ion cells using multi-dimensional laser scanning, Journal of The Electrochemical Society, Vol: 166, Pages: A27-A34, ISSN: 1945-7111
The safety, performance and lifetime of lithium-ion cells are critical for the acceptance of electric vehicles (EVs) but the detection of cell quality issues non-destructively is difficult. In this work, we demonstrate the use of a multi-dimensional laser scanning method to detect local inhomogeneities. Commercially available cells with Nickel Cobalt Manganese (NMC) cathode are cycled at various charge and discharge rates, while 2D battery displacement measurements are taken using the laser scanning system. Significant local swelling points are found on the cell during the discharge phase, the magnitude of swelling can be up to 2% of the cell thickness. The results show that the swelling can be aggravated by a combination of slow charge rate and fast discharge rate. Disassembly of the cells shows that the swelling points are matched with the location of ‘adhesive-like’ material found on the electrode surfaces. Scanning Electron Microscope (SEM) images show that the material is potentially blocking the electrodes and separators at these locations. We therefore present laser-scanning displacement as a valuable tool for defect/inhomogeneity detection.
Journal articleZhao Y, Patel Y, Zhang T, et al., 2018,
Modeling the effects of thermal gradients induced by tab and surface cooling on lithium ion cell performance, Journal of The Electrochemical Society, Vol: 165, Pages: A3169-A3178, ISSN: 0013-4651
Lithium ion batteries are increasingly important in large scale applications where thermal management is critical for safety and lifetime. Yet, the effect of different thermal boundary conditions on the performance and lifetime is still not fully understood. In this work, a two-dimensional electro-thermal model is developed to simulate cell performance and internal states under complex thermal boundary conditions. Attention was paid to model, not only the electrode stack but also the non-core components (e.g. tab weld points) and thermal boundaries, but also the experiments required to parameterize the thermal model, and the reversible heat generation. The model is comprehensively validated and the performance of tab and surface cooling strategies was evaluated across a wide range of operating conditions. Surface cooling was shown to keep the cell at a lower average temperature, but with a large thermal gradient for high C rates. Tab cooling provided much smaller thermal gradients but higher average temperatures caused by lower heat removing ability. The thermal resistance between the current collectors and tabs was found to be the most significant heat transfer bottleneck and efforts to improve this could have significant positive impacts on the performance of li-ion batteries considering the other advantages of tab cooling.
Journal articleMerla Y, Wu B, Yufit V, et al., 2018,
An easy-to-parameterise physics-informed battery model and its application towards lithium-ion battery cell design, diagnosis, and degradation, Journal of Power Sources, Vol: 384, Pages: 66-79, ISSN: 0378-7753
Accurate diagnosis of lithium ion battery state-of-health (SOH) is of significant value for many applications, to improve performance, extend life and increase safety. However, in-situ or in-operando diagnosis of SOH often requires robust models. There are many models available however these often require expensive-to-measure ex-situ parameters and/or contain unmeasurable parameters that were fitted/assumed. In this work, we have developed a new empirically parameterised physics-informed equivalent circuit model. Its modular construction and low-cost parametrisation requirements allow end users to parameterise cells quickly and easily. The model is accurate to 19.6 mV for dynamic loads without any global fitting/optimisation, only that of the individual elements. The consequences of various degradation mechanisms are simulated, and the impact of a degraded cell on pack performance is explored, validated by comparison with experiment. Results show that an aged cell in a parallel pack does not have a noticeable effect on the available capacity of other cells in the pack. The model shows that cells perform better when electrodes are more porous towards the separator and have a uniform particle size distribution, validated by comparison with published data. The model is provided with this publication for readers to use.
Journal articleZhang X-F, Zhao Y, Liu H-Y, et al., 2018,
Journal articleLiu X, Naylor Marlow M, Cooper S, et al., 2018,
We present an all-fiber flexible supercapacitor with composite nanofiber electrodes made via electrospinning and an electrospun separator. With the addition of manganese acetylacetonate (MnACAC) to polyacrylonitrile (PAN) as a precursor for the electrospinning process and subsequent heat treatment, the performance of pure PAN supercapacitors was improved from 90 F.g-1 to 200 F.g-1 (2.5 mV.s-1) with possible mass loadings of MnACAC demonstrated as high as 40 wt%. X-ray diffraction measurements showed that after thermal treatment, the MnACAC was converted to MnO, meanwile, the thermal decomposition of MnACAC increased the graphitic degree of the carbonised PAN. Scanning electron microscopy and image processing showed that static electrospinning of pure PAN and PAN-Mn resulted in fiber diameters of 460 nm and 480 nm respectively after carbonisation. Further analysis showed that the fiber orientation exhibited a slight bias which was amplified with the addition of MnACAC. Use of focused ion beam scanning electron microscopy tomography also showed that MnO particles were evenly distributed through the fiber at low MnACAC concentrations, while at a 40 wt% loading the MnO particles were also visible on the surface. Comparison of the electrospun separators showed improved performance relative to a commercial Celgard separator (200 F.g-1 vs 141 F.g-1).
Journal articleFew SPM, Schmidt O, Offer GJ, et al., 2018,
Prospective improvements in cost and cycle life of off-grid lithium-ion battery packs: An analysis informed by expert elicitations, Energy Policy, Vol: 114, Pages: 578-590, ISSN: 0301-4215
This paper presents probabilistic estimates of the 2020 and 2030 cost and cycle life of lithium-ion battery (LiB) packs for off-grid stationary electricity storage made by leading battery experts from academia and industry, and insights on the role of public research and development (R&D) funding and other drivers in determining these. By 2020, experts expect developments to arise chiefly through engineering, manufacturing and incremental chemistry changes, and expect additional R&D funding to have little impact on cost. By 2030, experts indicate that more fundamental chemistry changes are possible, particularly under higher R&D funding scenarios, but are not inevitable. Experts suggest that significant improvements in cycle life (eg. doubling or greater) are more achievable than in cost, particularly by 2020, and that R&D could play a greater role in driving these. Experts expressed some concern, but had relatively little knowledge, of the environmental impact of LiBs. Analysis is conducted of the implications of prospective LiB improvements for the competitiveness of solar photovoltaic + LiB systems for off-grid electrification.
Journal articleMarinescu M, O'Neill L, Zhang T, et al., 2018,
Irreversible vs reversible capacity fade of lithium-sulfur batteries during cycling: the effects of precipitation and shuttle, Journal of The Electrochemical Society, Vol: 165, Pages: A6107-A6118, ISSN: 1945-7111
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.
Journal articleArdani MI, Patel Y, Siddiq A, et al., 2017,
Combined experimental and numerical evaluation of the differences between convective and conductive thermal control on the performance of a lithium ion cell, Energy, Vol: 144, Pages: 81-97, ISSN: 0360-5442
Testing of lithium ion batteries is necessary in order to understand their performance, to parameterise and furthermore validate models to predict their behaviour. Tests of this nature are normally conducted in thermal/climate chambers which use forced air convection to distribute heat. However, as they control air temperature, and cannot easily adapt to the changing rate of heat generated within a cell, it is very difficult to maintain constant cell temperatures. This paper describes a novel conductive thermal management system which maintains cell temperature reliably whilst also minimising thermal gradients. We show the thermal gradient effect towards cell performance is pronounced below operating temperature of 25 °C at 2-C discharge under forced air convection. The predicted internal cell temperature can be up to 4 °C hotter than the surface temperature at 5 °C ambient condition and eventually causes layers to be discharge at different current rates. The new conductive method reduces external temperature deviations of the cell to within 1.5 °C, providing much more reliable data for parameterising a thermally discretised model. This method demonstrates the errors in estimating physiochemical paramet ers; notably diffusion coefficients, can be up to four times smaller as compared to parameterisation based on convective test data.
Journal articleHunt I, Zhang T, Patel Y, et al., 2017,
The effect of thermal gradients on the performance and cycle life of Li-S batteries is studied using bespoke single-layer Li-S cells, with isothermal boundary conditions maintained by Peltier elements. A temperature difference is shown to cause significant current imbalance between parallel connected single-layer cells, causing the hotter cell to provide more charge and discharge capacities during cycling. During charge, significant shuttle is induced in the hotter Li-S cell, causing accelerated degradation of it. A bespoke multi-tab cell in which the inner layers are electrically connected to different tabs versus the outer layers, is used to demonstrate that noticeable current inhomogeneity occurs during the operation of practical multilayer Li-S pouch cells, which is expected to affect their performance and degradation. The observed thermal and current inhomogeneity should have a direct consequence on battery pack and thermal management system design for real world Li-S battery packs.
Journal articleShibagaki T, Merla Y, Offer GJ, 2017,
Diagnosing the state-of-health of lithium ion batteries in-operando is becoming increasingly important for multiple applications. We report the application of differential thermal voltammetry (DTV) to lithium iron phosphate (LFP) cells for the first time, and demonstrate that the technique is capable of diagnosing degradation in a similar way to incremental capacity analysis (ICA). DTV has the advantage of not requiring current and works for multiple cells in parallel, and is less sensitive to temperature introducing errors. Cells were aged by holding at 100% SOC or cycling at 1C charge, 6D discharge, both at an elevated temperature of 45 °C under forced air convection. Cells were periodically characterised, measuring capacity fade, resistance increase (power fade), and DTV fingerprints. The DTV results for both cells correlated well with both capacity and power, suggesting they could be used to diagnose SOH in-operando for both charge and discharge. The DTV peak-to-peak capacity correlated well with total capacity fade for the cycled cell, suggesting that it should be possible to estimate SOC and SOH from DTV for incomplete cycles within the voltage hysteresis region of an LFP cell.
Journal articleCleaver T, Kovacik P, Marinescu M, et al., 2017,
A picture of the challenges faced by the lithium-sulfur technology and the activities pursued by the research community to solve them is synthesized based on 1992 scientific articles. It is shown that, against its own advice of adopting a balanced approach to development, the community has instead focused work on the cathode. To help direct future work, key areas of neglected research are highlighted, including cell operation studies, modelling, anode, electrolyte and production methods, as well as development goals for real world target applications such as high altitude unmanned aerial vehicles.
Journal articleZhao Y, Patel Y, Hunt IA, et al., 2017,
Lithium-ion cells can unintentionally be exposed to temperatures outside manufacturers recommended limits without triggering a full thermal runaway event. The question addressed in this paper is: Are these cells still safe to use? In this study, externally applied compression has been employed to prevent lithium ion battery failure during such events. Commercially available cells with Nickel Cobalt Manganese (NCM) cathodes were exposed to temperatures at 80 °C, 90 °C and 100 °C for 10 h, and electrochemically characterised before and after heating. The electrode stack structures were also examined using x-ray computed tomography (CT), and post-mortems were conducted to examine the electrode stack structure and surface changes. The results show that compression reduces capacity loss by −0.07%, 4.95% and 13.10% respectively, measured immediately after the thermal testing. The uncompressed cells at 80 °C showed no swelling, whilst 90 °C and 100 °C showed significant swelling. The X-ray CT showed that the uncompressed cell at 100 °C suffered de-lamination at multiple locations after test, and precipitations were found on the electrode surface. The post-mortem results indicates the compressed cell at 100 °C was kept tightly packed, and the electrode surface was uniform. The conclusion is that externally applied compression reduces delamination due to gas generation during high temperature excursions.
Book chapterWu B, Offer G, 2017,
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.
Journal articleZhang T, Marinescu M, Walus S, et al., 2017,
What Limits the Rate Capability of Li-S Batteries during Discharge: Charge Transfer or Mass Transfer?, Journal of the Electrochemical Society, Vol: 165, Pages: A6001-A6004, ISSN: 0013-4651
Li-S batteries exhibit poor rate capability under lean electrolyte conditions required for achieving high practical energy densities. In this contribution, we argue that the rate capability of commercially-viable Li-S batteries is mainly limited by mass transfer rather than charge transfer during discharge. We first present experimental evidence showing that the charge-transfer resistance of Li-S batteries and hence the cathode surface covered by Li2S are proportional to the state-of-charge (SoC) and not to the current, directly contradicting previous theories. We further demonstrate that the observed Li-S behaviors for different discharge rates are qualitatively captured by a zero-dimensional Li-S model with transport-limited reaction currents. This is the first Li-S model to also reproduce the characteristic overshoot in voltage at the beginning of charge, suggesting its cause is the increase in charge transfer resistance brought by Li2S precipitation.
Journal articleWalus S, Offer GJ, Hunt I, et al., 2017,
Volumetric expansion of Lithium-Sulfur cell during operation – Fundamental insight into applicable characteristics, Energy Storage Materials, Vol: 10, Pages: 233-245, ISSN: 2405-8297
During the operation of a Lithium-Sulfur (Li-S) cell, structural changes take place within both positive and negative electrodes. During discharge, the sulfur cathode expands as solid products (mainly Li2S or Li2S/Li2S2) are precipitated on its surface, whereas metallic Li anode contracts due to Li oxidation/stripping. The opposite processes occur during charge, where Li anode tends to expand due to lithium plating and solid precipitates from the cathode side are removed, causing its thickness to decrease. Most research literature describe these processes as they occur within single electrode cell constructions. Since a large format Li-S pouch cell is composed of multiple layers of electrodes stacked together, and antagonistic effects (i.e. expansion and shrinkage) occur simultaneously during both charge and discharge, it is important to investigate the volumetric changes of a complete cell. Herein, we report for the first time the thickness variation of a Li-S pouch cell prototype. In these studies we used a laser gauge for monitoring the cell thickness variation under operation. The effects of different voltage windows as well as discharge regimes are explored. It was found that the thickness evolution of a complete pouch cell is mostly governed by Li anodes volume changes, which mask the response of the sulfur cathodes. Interesting findings on cell swelling when cycled at slow currents and full voltage windows are presented. A correlation between capacity retention and cell thickness variation is demonstrated, which could be potentially incorporated into Battery Management System (BMS) design for Li-S batteries.
Journal articleZhang X-F, Zhao Y, Patel Y, et al., 2017,
Journal articleHunt IA, Patel Y, Szczygielski M, et al., 2015,
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