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Conditions such as the temperature and pressure experienced by lithium-ion battery components are dependent on cell geometry and can vary widely within a large cell. The resulting uneven degradation is challenging to study at the full cell level but can be revealed upon disassembly and post mortem analysis. In this work, we report localized lithium plating in automotive-grade, prismatic lithium-ion cells, also under cycling conditions generally considered to be mild (e.g., 5–65 %SOC, 23 °C, 0.5C cycle rate). Dead lithium content is quantified using 7Li nuclear magnetic resonance spectroscopy in both electrode and separator samples, corresponding to substantial capacity fade (26–46%) of the full cells. Severe lithium plating is typically initiated in regions near the positive tab, in which both the separators and negative electrodes are ultimately deactivated. High pressure arises during cycling, and we propose a deactivation mechanism based on high local stress due to electrode expansion and external constraint. Further, we develop a model to demonstrate that component deactivation can result in lithium plating even under mild cycling conditions. Notably, components harvested from regions with no detected lithium plating maintained adequate electrochemical performance.

Lithium ion batteries (LIB) have become a cornerstone of the shift to electric transportation. In an attempt to decrease the production load and prolong battery life, understanding different degradation mechanisms in state-of-the-art LIBs is essential. Here, we analyze how operational temperature and state-of-charge (SoC) range in cycling influence the ageing of automotive grade 21700 batteries, extracted from a Tesla 3 long Range 2018 battery pack with positive electrode containing LiNixCoyAlzO2 (NCA) and negative electrode containing SiOx-C. In the given study we use a combination of electrochemical and material analysis to understand degradation sources in the cell. Herein we show that loss of lithium inventory is the main degradation mode in the cells, with loss of material on the negative electrode as there is a significant contributor when cycled in the low SoC range. Degradation of NCA dominates at elevated temperatures with combination of cycling to high SoC (beyond 50%)., QC 20230901

Using stainless steel as material for bipolar plates (BPPs) in proton exchange membrane fuel cells (PEMFCs) carries a perceived risk of corrosion and subsequent metal ion contamination of the membrane electrode as-sembly (MEA). However, assessments in literature on this hazard to PEMFC systems have been based on ex-situ corrosion studies, where general assumptions made on the BPP environment might not be a correct simulation of real on-site conditions. In this contribution, uncoated BPPs from stainless steel grades 304 L, 316 L and 904 L were subjected to in-situ hybrid endurance/stress testing to simulate realistic conditions in operating fuel cell systems and re-evaluate the need of additional corrosion protection. A post analysis of the plates showed no signs of surface dissolution on any of the tested samples and the concentration of iron in the MEA averaged 7 to 10 ppm for uncoated samples and 7 to 11 ppm for coated and graphitic reference tests, displaying a negligible amount of trace metals compared to critical thresholds found in literature. Contact resistance values were stable for all samples and observable changes in cell performance and voltage degradation was confirmed to be un-related to the presence of uncoated bipolar plates. The combined effects of decoupling of bipolar plate surface potentials from electrode potentials and operational control of stable gas flow compositions to sustain stainless steel surface passivation, were identified as explanation for the experimentally observed corrosion resistance of uncoated stainless steel plates in PEMFCs., QC 20230904

The integration of proton exchange membrane fuel cells (PEMFCs) in heavy-duty vehicles would be facilitated if operating temperatures above 100 degrees C were possible. In this work, the effect of temperature in the intermediate range of 80-120 degrees C is investigated for a commercial membrane electrode assembly (MEA) through polarization curves and electrochemical impedance spectroscopy. The importance of oxygen partial pressure on voltage is systematically studied by decoupling it from humidity and temperature. The results show that adequate oper-ation at intermediate temperature is achievable if the oxygen partial pressure is sufficient. Although the cathode kinetics is faster with rising temperatures, the voltage gain is counteracted by the decreasing equilibrium po-tential. At intermediate temperature, the water transport is enhanced, levelling out the relative humidity dif-ference between anode and cathode. However, ionic conductivity in the polymer can become limiting at high currents, due to a smaller relative humidity increase at these temperatures. To conclude, a higher operating temperature does not inherently cause a decrease in obtained current density. Rather, the difficulty to simul-taneously have sufficient oxygen partial pressure and high relative humidity causes limitations within the cathode that to some extent can be solved by pressurizing the cell., QC 20230620

The vanadium redox flow battery (VRFB) is a promising and commercially available technology that poses advantageous features for stationary energy storage. A key component of the VRFB in terms of cost and system efficiency is the membrane. In recent years, anion exchange membranes (AEMs) have gained interest in VRFB research as they in general exhibit lower vanadium crossover due to a more substantial Donnan exclusion effect. In this study, a low-resistance flow cell was developed and the electrochemical performance of Aemion (TM) anion exchange membranes AF1-HNN5-50-X, AF1-HNN8-50-X and AF1-ENN8-50-X were compared against commonly used cation exchange membranes, Nafion(R) 211 and 212. The VRFB using AF1-ENN8-50-X exhibited superior performance versus Nafion(R) 212 regarding cycling efficiency and rate performance. However, relatively high and comparable capacity losses were observed using both membranes. NMR analysis showed no sign of chemical degradation for AF1-ENN8-50-X by immersion in VO2+ solution for 800 h. Although Aemion (TM) AEMs showed good chemical and electrochemical performance, considerable electrolyte crossover was observed due to high water uptake., QC 20220321

To promote the development of anion exchange membrane fuel cells (AEMFC), an understanding of the oxygen reduction reaction (ORR) kinetics in porous gas diffusion electrodes is essential. In this work, experimental polarisation curves for electrodes with different platinum catalyst loadings and oxygen partial pressures at the cathode are fitted to a physics-based porous electrode model in the voltage range from open circuit voltage (OCV) to 0.7 V. Polarisation curves measured with different anode catalyst loadings, and hydrogen partial pressures, were used to verify the model. The reactions are described using a two-step Tafel-Volmer pathway at the anode and concentration-dependent Butler-Volmer kinetics at the cathode. A good fit to experimental data in the kinetic region is obtained with an exchange current density of 1.0.10(-8)Acm(-2), a first order dependency on oxygen partial pressure, and a charge transfer coefficient of 0.8 for the ORR. For lower oxygen partial pressure, hydrogen crossover is needed to explain the downward shift of the polarisation curves in the kinetic region. In the experimental data, the polarisation curves show an apparent limiting current density at lower hydrogen partial pressures, explained by the lower rate of the Tafel step at these conditions., QC 20211223

Trace-metal contamination poses a threat to performance and stability of proton exchange membrane fuel cells (PEMFCs). In this study the source of origin and degree of metal dissolution from carbon-coated 316L bipolar plates (BPPs) are evaluated after a long-term PEMFC test run under conditions resembling a real-life automotive application. Despite intact carbon-coating, metal dissolution occurs from uncoated oxycarbide stains on the plates? surface. Which correlates with post-mortem detection of chromium, iron and nickel in the membrane electrode assembly. The rate of cell voltage decrease throughout the high current operations is found to be twice as high in the presence of metal ions. Metal dissolution can be correlated with transients in cell voltage during dynamic current load cycling as a result of temporary global fuel starvation. The observed difference in metal dissolution on the anode and cathode BPP indicates weak galvanic coupling between the bipolar plate(s) and the electrode layer(s). ? 2020 The Authors. Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC. This is an open access article under the CC BY license (http://creativecommons.org/ licenses/by/4.0/)., QC 20210531

The hydrogen electrode in the anion-exchange membrane fuel cell needs further attention to understand the overall cell limitations. In this study, electrochemical impedance spectroscopy and galvanodynamic measurements in combination with a physics-based model are used to determine the kinetic parameters of the hydrogen oxidation reaction and hydrogen evolution reaction on Pt/C porous gas-diffusion electrodes in an AEMFC. Two semicircles are observed in the Nyquist plot of a symmetrical AEM hydrogen cell, indicating a two-step reaction pathway. The fit of the model shows that the Tafel-Volmer pathway describes the kinetics better than the Heyrovsky-Volmer pathway. The reaction rates of the adsorption and charge transfer steps are similar in magnitude implying that both need consideration during modeling and evaluation of the hydrogen electrode. Furthermore, the performance is limited also by the ionic conductivity in the electrode. Comparison of the impedance of the HOR and a hydrogen/oxygen AEMFC indicates that the low-frequency semicircle is mainly associated with the oxygen reduction reaction and the cathode, while the high-frequency semicircle is likely related to a combination of the anode and the cathode. Based on this work, a platform for further studies of losses and total impedance of operating AEMFC has been created., QC 20210414

Four novel poly(phenylene oxide)-based anion exchange membranes were investigated for electrochemical performance, ionic conductivity and water transport properties in an operating anion exchange membrane fuel cell (AEMFC), using Pt/C gas diffusion electrodes with Tokuyama ionomer. The poly(phenylene oxide)-membranes have a 1- or 5-carbon alkyl spacer between the backbone and a trimethylalkylammonium (TMA) or piperidinium (Pip) cationic group, and ion-exchange capacities (IECs) between 1.5 and 1.9 mequiv g(-1). The polymer with a 5-carbon alkyl spacer, a TMA cationic group, and a higher IEC showed the highest ion conductivity and performance in the AEMFC. The results also show that introducing a 5-carbon alkyl spacer does not improve performance unless the IEC is increased and that exchanging the TMA with a Pip cationic group results in lower fuel cell performance despite a higher IEC. A discrepancy in ion conductivity between fuel cell and ex situ test was observed for the 5-carbon spacer polymers and is attributed to a higher sensitivity for dehydration. Similar water flux under load, from the anode to the cathode with increased water content at both electrodes, was observed for all membranes and only varied with membrane thickness. The deviation in fuel cell performance observed between the membranes could not be explained by differences in water flux or ionic conduction, suggesting that the electrode-membrane interaction plays a major role. Nevertheless, the study emphasizes that high membrane conductivity (for the lambda-range in a fuel cell) and efficient water transport (obtained by lower membrane thickness) promote higher electrochemical performance., QC 20200608

There is a strong need to develop purification methods for textile industrial wastewater containing toxic azo dyes. The reductive cleavage of azo dyes can be made by anaerobic bacteria, but the products of aromatic amines require an aerobic process. In this study a novel bacterial dye degrading consortium (DDC) of five isolated strains identified with 16S rRNA sequence: Proteus mirabilis (KR732288), Bacillus anthracis (KR732289), Enterobacter hormaechei (KR732290), Pseudomonas aeruginosa (KR732293) and Serratia rubidaea (KR732296) were used to aerobically decompose metabolite 2-aminobenxenesulfonic acid (2-ABS), as a model compound. The effect of three variables: temperature (28-42 degrees C), pH (5.0-8.0) and initial concentration of 2-ABS (5-40 ppm) was investigated in terms of degradation and chemical oxygen demand (COD) removal. Central composite design matrixand response surface methodology (RSM) were used for experimental design to evaluate theinteraction of the three process variables. The results show that up to 95% degradation and COD 90% removal are possible at optimal values of 32.4 ppm 2-ABS, pH 6.6 and a temperature of 35.7 degrees C. The theoretical response variables predicted by the developed RSM model was supported the experimental results. The optimized degradation of 2-ABS and COD removal were further confirmed by UV-HPLC analysis., QC 20200713

Pt-supported on multi-walled carbon nanotubes (MWCNT) and N-modified MWCNT (N-MWCNT) catalysts are synthesized by pyrolysis from emeraldine solution and microemulsion. Their electrochemical properties and carbon corrosion resistance in a Proton Exchange Membrane Fuel Cell (PEMFC) are compared with a commercial Pt/Vulcan catalyst through I–V curves, cyclic voltammetry and CO stripping. The initial fuel cell performances of the Pt/(N-)MWCNT catalysts are superior to Pt/Vulcan. The corrosion of the catalysts is quantified by the continuous measure of the CO2 release by online-mass spectrometry during potentiodynamic cycling between 0.1 and 1.6 V at 80 °C. The results show that Pt/MWCNT (with the lowest double-layer capacity) is the most stable catalyst followed by Pt/N-MWCNT and Pt/Vulcan, initially losing carbon at a rate of 1.1, 3.4 and 4.7 μgC (mg Ctot)−1 cycle−1, respectively. After about 30% carbon loss (50–70 cycles) all catalysts corrode at an approximate rate of 5.5 μgC mg−1 cycle−1. At this stage, all show similar electrochemical surface area and double-layer capacity. However, the substantial diminution of the initially very thick and porous Pt/(N-)MWCNT catalyst layers after corrosion consequences in lower fuel cell performance compared to the structurally less affected Pt/Vulcan electrode. The results clearly reveal that CNT-based catalyst supports are more corrosion resistant compared to state-of-the-art Vulcan. Moreover, the performance of the corroded electrodes envisages the importance of electrode porosity., QC 20200304

Understanding limitations in an operating AEMFC is essential to .enhance the technology. Here the electrode processes are studied experimentally as well as by two physics-based models taking the porosity of the electrodes into account. The aim is to use the models to determine kinetic parameters specific for in-situ operation. The models can also be used to explain the experimental .behavior. From the impedance model of a symmetric H2/H2 cell it is shown that the hydrogen oxidation reaction (HOR) proceeds through the Tafel-Volmer reaction pathway, with the hydrogen adsorption as the slower reaction step. Based on the HOR model a •steady-state model of an O2/H2 cell is used to evaluate data from 14 experimental I-V curves, obtained for different gas partial pressures and catalyst loadings, in order to study the effects of the oxygen reduction reaction and overall cell limitations. The results show that the oxygen reduction reaction kinetics limit the cell performance for low current densities. However, at higher currents the uneven current distribution and locally low hydrogen adsorption at the anode increasingly affect the overall performance. Uneven current distribution is also observed at the cathode and likely caused by insufficient effective ionomer conductivity., QC 20200506

Sufficient water transport through the membrane is necessary for a well-performing anion exchange membrane fuel cell (AEMFC). In this study, the water flux through a membrane electrode assembly (MEA), using a Tokuyama A201 membrane, is quantified using humidity sensors at the in- and outlet on both sides of the MEA. Experiments performed in humidified inert gas at both sides of the MEA or with liquid water at one side shows that the aggregation state of water has a large impact on the transport properties. The water fluxes are shown to be approximately three times larger for a membrane in contact with liquid water compared to vaporous. Further, the flux during fuel cell operation is investigated and shows that the transport rate of water in the membrane is affected by an applied current. The water vapor content increases on both the anode and cathode side of the AEMFC for all investigated current densities. Through modeling, an apparent water drag coefficient is determined to −0.64, indicating that the current-induced transport of water occurs in the opposite direction to the transport of hydroxide ions. These results implicate that flooding, on one or both electrodes, is a larger concern than dry-out in an AEMFC., QC 20190306

The performance of thin carboxylated cellulose nanofiber-based (CNF) membranes as proton exchange membranes in fuel cells has been measured in situ as a function of CNF surface charge density (600 and 1550 mu mol g(-1)), counterion (H+ or Na+), membrane thickness and fuel cell relative humidity (RH 55 to 95%). The structural evolution of the membranes as a function of RH, as measured by Small Angle X-ray Scattering, shows that water channels are formed only above 75% RH. The amount of absorbed water was shown to depend on the membrane surface charge and counter ions (H+ or Na+). The high affinity of CNF for water and the high aspect ratio of the nanofibers, together with a well-defined and homogenous membrane structure, ensures a proton conductivity exceeding 1 mS cm(-1) at 30 degrees C between 65 and 95% RH. This is two orders of magnitude larger than previously reported values for cellulose materials and only one order of magnitude lower than Nafion 212. Moreover, the CNF membranes are characterized by a lower hydrogen crossover than Nafion, despite being approximate to 30% thinner. Thanks to their environmental compatibility and promising fuel cell performance the CNF membranes should be considered for new generation proton exchange membrane fuel cells.

Fuel cells are foreseen to have an important role in sustainable energy systems, provided that catalysts with higher activity and stability are developed. In this study, highly active sputtered thin films of platinum alloyed with yttrium (Pt3Y) are deposited on commercial gas diffusion layers and their performance in a proton exchange membrane fuel cell is measured. After acid pretreatment, the alloy is found to have up to 2.5 times higher specific activity than pure platinum. The performance of Pt3Y is much higher than that of pure Pt, even if all of the alloying element was leached out from parts of the thin metal film on the porous support. This indicates that an even higher performance is expected if the structure of the Pt3Y catalyst or the support could be further improved. The results show that platinum alloyed with rare earth metals can be used as highly active cathode catalyst materials, and significantly reduce the amount of platinum needed, in real fuel cells., QC 20180529

The effects of external compression on the performance and ageing of NMC(1/3)/Graphite single-layer Li-ion pouch cells are investigated using a spring-loaded fixture. The influence of pressure (0.66, 0.99, 1.32, and 1.98 MPa) on impedance is characterized in fresh cells that are subsequently cycled at the given pressure levels. The aged cells are analyzed for capacity fade and impedance rise at the cell and electrode level. The effect of pressure distribution that may occur in large-format cells or in a battery pack is simulated using parallel connected cells. The results show that the kinetic and mass transport resistance increases with pressure in a fresh cell. An optimum pressure around 1.3 MPa is shown to be beneficial to reduce cyclable-lithium loss during cycling. The minor active mass losses observed in the electrodes are independent of the ageing pressure, whereas ageing pressure affects the charge transfer resistance of both NMC and graphite electrodes and the ohmic resistance of the cell. Pressure distribution induces current distribution but the enhanced current throughput at lower pressures cell does not accelerate its ageing. Conclusions from this work can explain some of the discrepancies in non-uniform ageing reported in the literature and indicate coupling between electrochemistry and mechanics., QC 20180321

The performance and durability of 316L stainless steel bipolar plates (BPP) electroplated with Ni–Mo and Ni–Mo–P coatings are investigated in a proton exchange membrane fuel cell (PEMFC), using a commercial Pt/C Nafion membrane electrode assembly (MEA). The effect of the BPP coatings on the electrochemical performance up to 115 h is evaluated from polarization curves, cyclic voltammetry and electrochemical impedance spectroscopy together with interfacial contact resistance (ICR) measurements between the coatings and the gas diffusion layer. The results show that all the coatings decrease the ICR in comparison to that of uncoated 316L BPP. The Ni-Mo coated BPP shows a low and stable ICR and the smallest effects on MEA performance, including catalyst activity/usability, cathode double layer capacitance, and membrane and ionomer resistance build up with time. After electrochemical evaluation, the BPPs as well as the water effluents from the cell are examined by Scanning Electron Microscopy, Energy Dispersive and Inductively Coupled Plasma spectroscopies. No significant degradation of the coated surface or enhancement in metal release is observed. However, phosphorus addition to the coating does not show to improve its properties, as deterioration of the MEA and consequently fuel cell performance losses is observed., QC 20171023