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At least 199 records · Page 11

LaCoO 3-δ coated Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ cathode for intermediate temperature solid oxide fuel cells

Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ (BSCF) is a promising cathode for intermediate temperature solid oxide fuel cells. Yet, BSCF cathode performance stability has been a challenge and its electrochemical performance deteriorates severely in the presence of Cr2O3-forming metallic interconnect. We demonstrate that LaCoO 3-δ (LC) coating on BSCF cathode can not only enhance BSCF electrochemical performance, but also effectively improve the BSCF performance stability. Here, LC-coated BSCF-Gd 0.1 Ce 0.9 O 1.9 (LC@BSCF-GDC) cathode is prepared through a solution impregnation method and systematically characterized. EIS, XRD, Raman, SEM and EDS tests with and without SUS430 interconnect are conducted to characterize the Cr-tolerance. The results reflect that BSCF-GDC cathode is susceptible to Cr poisoning while LC@BSCF-GDC cathode has significantly enhanced tolerance to Cr poisoning. Single cells with LC@BSCF-GDC cathode achieve higher peak power density and smaller polarization resistance values than that of single cells with BSCF-GDC cathode. Furthermore, significant improvement of performance stability under a constant current load has been achieved for single cells with LC@BSCF-GDC cathode. This work provides a new solution for solving BSCF cathode performance stability.

25 ENERGY STORAGE↗

Solvent-Free Melt-Processed Cathode Mitigates Li Anode Instability in Polymer-Based Solid-State Batteries

Solvent-free manufacturing of battery components is a promising alternative to traditional slurry processing for reducing the cost and environmental impact. In this work, we used twin-screw melt extrusion to fabricate a polymer-based high voltage composite cathode. The melt-processed cathode is dense (near zero porosity) and thick (65 μm) and has high active material loading (80 wt %). The active particles are distributed uniformly throughout the melt-processed cathode, unlike the traditional slurry-cast cathode, which exhibits inhomogeneous particle distribution. In the melt-processed cathode, polymer and carbon form separate phases, whereas in the slurry-cast cathode they blend into a single phase. Due to these structural differences, the melt-processed cathode shows smooth charge–discharge profiles, while the slurry-cast cathode shows noisy charging and soft-shorting behavior. In conclusion, this work highlights that twin-screw extrusion as a scalable, solvent-free manufacturing method is advantageous in producing uniform cathodes, which mitigates anode instability.

25 ENERGY STORAGE↗

Designing the Platinum Catalyst Layer for Improved Performance and Durability in Anion Exchange Membrane Water Electrolysis

To lower the cost of hydrogen produced by anion exchange membrane water electrolysis (AEMWE), it is critical to reduce the use of platinum group metal (PGM) catalysts within the device. While iridium has been successfully replaced with PGM-free catalysts at the anode, platinum-based (Pt) cathode catalysts are still required to meet the activity and durability targets. This study investigates the impact of commercial Pt/C catalyst loading, ionomer type and content, and electrode fabrication method on the cathode catalyst layer properties and AEMWE performance with the aim of determining the feasibility of reduced Pt loadings. While increased Pt loading is found to improve beginning-of-life performance, the effects are minimal above 0.6 mg/cm 2 . Ink characterization shows that ionomer type and content affect the ink stability, particle size, and percent of unbound ionomer, which further impact the homogeneity of the sprayed catalyst layers. The 5% PiperION cathode exhibited the highest performance, which may be attributed to a balance between the small particle size and the low proportion of unbound ionomer, minimizing kinetic and transport losses. Theoretical calculations show that the ionomers interact differently with the Pt surface, causing different surface charges and water adsorption strength and activating different mechanisms for hydrogen evolution. Pt-PiperION lowered the enthalpy of water-splitting by 0.1 eV compared to Pt alone and allowed for equal site access between adsorbed H* and OH* (both adsorbed at circa −2.2 eV). Although catalyst-coated membrane (CCM) fabrication techniques are desirable for scale-up, no performance enhancement is observed compared with the catalyst-coated substrate approach. Durability, as measured by degradation rates, Pt loss, and catalyst layer restructuring, was found to improve with increased Pt loadings, higher ionomer content, and CCM architectures. These findings provide important insight into the significant role of the cathode in AEMWE and strategies for maintaining the performance with low Pt loading or PGM-free catalysts.

08 HYDROGEN↗

A Facile, Low-Cost Hot-Pressing Process for Fabricating Lithium-Sulfur Cells with Stable Dynamic and Static Electrochemistry

Lithium–sulfur batteries are among the most promising low-cost, high-energy-density storage devices. However, the inability to host a sufficient amount of sulfur in the cathode while maintaining good electrochemical stability under a lean electrolyte condition has limited the progress. The main cause of these challenges is the sensitivity of the sulfur cathode to the cell-design parameters (i.e., the amount of sulfur and electrolyte) and the experimental testing conditions (i.e., cycling rates and analysis duration). Here, a hot-pressing method is presented that effectively encapsulates a high amount of sulfur in the cathode within only 5 s, resulting in high sulfur loading and content of, respectively, 10 mg cm -2 and 65 wt%. The hot-pressed sulfur (HPS) cathodes exhibit superior dynamic and static electrochemical performance under a broad cycling-rate (C/20–1C rates) and low electrolyte/sulfur ratio (6 µL mg -1 ) conditions. The dynamic cell stability is demonstrated by high gravimetric and areal capacities of, respectively, 415–730 mAh g -1 and 7–12 mAh cm -2 at C/20–1C rates with a high capacity retention of over 70% after 200 cycles. As a result, the static cell stability is demonstrated by excellent shelf life with low self-discharge and stable cycle life on storing for over one year.

25 ENERGY STORAGE↗

Photo-driven growth of a monolayer of platinum spherical-nanocrowns uniformly coated on a membrane toward fuel cell applications

Membrane electrode assemblies (MEAs) serve as the core units of polymer electrolyte membrane fuel cells (PEMFCs) and are regularly fabricated by painting a slurry of commercial Pt/C onto a membrane, leading to thick and disordered electrocatalyst layers (CLs). Herein, we report a photo-driven fabrication of MEAs with ultra-thin and ordered CLs by growing a monolayer of dendritic platinum spherical nanocrowns onto each side of a photocatalyst-modified membrane. This approach allows us to control the thickness and platinum loading of ordered CLs by simply varying the concentration of the platinum precursor under tungsten light irradiation. The resultant MEAs exhibit an excellent fuel cell power density of 1.01 ± 0.05 W cm –2 at a platinum loading of 53 ± 1.5 μg cm cathode –2 . Furthermore, this exceptional activity likely arises from the nanostructured platinum crowns, efficient mass transport, and uniform reaction rate in the ultrathin (59 ± 12 nm thick) and ordered CLs according to electrochemical and theoretical investigations.

25 ENERGY STORAGE↗

Functionalization of Cathode–Electrolyte Interface with Ionic Liquids for High-Performance Quasi-Solid-State Lithium–Sulfur Batteries: A Low-Sulfur Loading Study

We introduce a quasi-solid-state electrolyte lithium-sulfur (Li–S) battery (QSSEB) based on a novel Li-argyrodite solid-state electrolyte (SSE), Super P–Sulfur cathode, and Li-anode. The cathode was prepared using a water-based carboxymethyl cellulose (CMC) solution and styrene butadiene rubber (SBR) as the binder while Li6PS5F0.5Cl0.5 SSE was synthesized using a solvent-based process, via the introduction of LiF into the argyrodite crystal structure, which enhances both the ionic conductivity and interface-stabilizing properties of the SSE. Ionic liquids (IL) were prepared using lithium bis(trifluoromethyl sulfonyl)imide (LiTFSI) as the salt, with pre-mixed pyrrolidinium bis(trifluoromethyl sulfonyl)imide (PYR) as solvent and 1,3-dioxolane (DOL) as diluent, and they were used to wet the SSE–electrode interfaces. The effect of IL dilution, the co-solvent amount, the LiTFSI concentration, the C rate at which the batteries are tested and the effect of the introduction of SSE in the cathode, were systematically studied and optimized to develop a QSSEB with higher capacity retention and cyclability. Interfacial reactions occurring at the cathode–SSE interface during cycling were also investigated using electrochemical impedance spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy supported by ab initio molecular dynamics simulations. This work offers a new insight into the intimate interfacial contacts between the SSE and carbon–sulfur cathodes, which are critical for improving the electrochemical performance of quasi-solid-state lithium–sulfur batteries.

25 ENERGY STORAGE↗

Hydrogen production from lignocellulosic hydrolysate in an up-scaled microbial electrolysis cell with stacked bio-electrodes

Hydrogen production from renewable resources via microbial electrolysis cells (MECs) is a promising approach for sustainable energy production. Yet high hydrogen yield from real feedstocks has not been demonstrated in up-scaled MECs. In this study, a 10-L single chamber MEC with a high electrode surface area to volume ratio (66 m 2 /m 3 ) was constructed and electroactive cathodic biofilms were enriched for hydrogen evolution reaction. A high hydrogen yield of 91% was achieved using lignocellulosic hydrolysate with a hydrogen production rate of 0.71 L/L/D at an organic loading rate of 0.4 g/D. The anodic and cathodic microbial communities, with Enterococcus spp. as the known electroactive bacteria, were capable of achieving current densities of 13.7 A/m 2 and 16.5 A/m 2 , respectively. Finally, a machine learning algorithm was used to investigate the correlation between community data and electrochemical performance, and the critical genera on determining current density were identified.

54 ENVIRONMENTAL SCIENCES↗

Understanding implications of cathode architecture on energy density of solid-state batteries

Next generation solid-state batteries (SSB) will need to leverage high voltage cathodes, as well as metallic anodes to achieve the realistic performance targets necessary to replace liquid electrolyte-based batteries in cutting-edge applications including electric vehicles. However, limitations arising from mass and charge transports, kinetics and chemo-mechanical degradation at the electrode | electrolyte interface limit the performance of present day SSBs. Optimizing composite cathode architecture, which is an integral part of solid-state batteries, is vital to realize the high-energy density and high-performance goals for next-generation solid-state batteries. Additionally, cathode architecture needs to be optimized for high loadings of active material, well-percolated ion and electron transport pathways and increased resilience against electrochemical stresses. This paper provides a first report of framework for geometric modeling of composite cathode architectures and evaluates the impact of cathode architecture on cell-level energy density using hierarchical models. Packing around primary and secondary active material particles are simulated for a range of active material particle size and solid electrolyte size distributions in the composite cathode. Impact of packing architecture on processing parameters of a given cathode composition and thickness, as well as on achievable energy density is evaluated for a range of commonly used solid electrolyte and cathode materials. Overall, the proposed framework offers a facile exploratory methodology for establishing initial metrics for scalable processing of practical and competent SSBs.

25 ENERGY STORAGE↗

Enabling High-Performance NASICON-Based Solid-State Lithium Metal Batteries Towards Practical Conditions

Solid-state lithium metal batteries (SSLMBs) are promising next-generation high-energy rechargeable batteries. However, the practical energy densities of the reported SSLMBs have been significantly overstated due to the use of thick solid-state electrolytes, thick lithium (Li) anodes, and thin cathodes. Here, a high-performance NASICON-based SSLMB using a thin (60 µm) Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) electrolyte, ultrathin (36 µm) Li metal, and high-loading (8 mg cm -2 ) LiFePO 4 (LFP) cathode is reported. The thin and dense LAGP electrolyte prepared by hot-pressing exhibits a high Li ionic conductivity of 1 × 10 -3 S cm -1 at 80 °C. The assembled SSLMB can thus deliver an increased areal capacity of ≈1 mAh cm -2 at C/5 with a high capacity retention of ≈96% after 50 cycles under 80 °C. Furthermore, it is revealed by synchrotron X-ray absorption spectroscopy and in situ high-energy X-ray diffraction that the side reactions between LAGP electrolyte and LFP cathode are significantly suppressed, while rational surface protection is required for Ni-rich layered cathodes. This study provides valuable insights and guidelines for the development of high-energy SSLMBs towards practical conditions.

25 ENERGY STORAGE↗

Multifunctional Utilization of Pitch-Coated Carbon Fibers in Lithium-Based Rechargeable Batteries

This work reports carbon fibers as an electrode material and current collector for dual-carbon and lithium-ion batteries. Here, fully graphitic and semigraphitic carbon fibers undergo anion intercalation beyond 4.5 V versus Li/Li + . Symmetric dual-carbon full cells using a pitch-coated fully graphitic carbon fiber mat as both cathode and anode delivers an energy-density of 276 and 322 Wh kg -1 at 342 W kg -1 power density in the voltage range of 3.0–5.0 and 3.0–5.2 V, respectively. On the other hand, nongraphitic carbon fibers do not exhibit anion intercalation up to 5.2 V and can be used as a current collector. They also possess a larger number of Li + storage sites in their randomly oriented microstructure when used as an anode. A lithium-ion full cell with double carbon-coated C-LiFePO 4 loaded on nongraphitic carbon fiber as a cathode and pitch-coated nongraphitic carbon fiber as an anode exhibits 202.6 and 75.2 Wh kg -1 energy density at power densities of 46.75 W kg -1 and 11.7 kW kg -1 , respectively in 2.0–3.5 V range. This pitch-coated carbon fiber-based battery configuration eliminates the need for metal foils and costly fluorinated binders, lowers overall weight of the cell, and is capable of sustaining mechanical stress and thermal shock.

PF6− intercalation↗

Highly flexible, freestanding tandem sulfur cathodes for foldable Li–S batteries with a high areal capacity

Li–S batteries with a high theoretical capacity are considered as the most promising candidate to satisfy the increasing demand for batteries with a high areal capacity. However, the low sulfur loading (<2 mg cm -2 ) and poor flexibility of current Li–S batteries limit their application in establishing foldable Li–S batteries with a high areal capacity. Here, to solve this problem, we employ here a free-standing flexible tandem sulfur cathode with a remarkably high sulfur loading to demonstrate foldable, high-areal-capacity Li–S batteries. The design of the tandem cathode readily increases the sulfur loading and effectively retards the migration of polysulfides. Therefore, the Li–S cell employing the tandem cathode exhibits a high initial areal capacity of 12.3 mA h cm -2 with stable cycling stability even with a high sulfur loading of up to 16 mg cm -2 . These tandem cathodes are promising for foldable Li–S cells with a high areal capacity and energy density.

25 ENERGY STORAGE↗

3D-Printed Graded Electrode with Ultrahigh MnO 2 Loading for Non-Aqueous Electrochemical Energy Storage

Electrolytic manganese dioxide is one of the promising cathode candidates for electrochemical energy storage devices due to its high redox capacity and ease of synthesis. Yet, high-loading MnO 2 often suffers from sluggish reaction kinetics, especially in non-aqueous electrolytes. The non-uniform deposition of MnO 2 on a porous current collectors also makes it difficult to fully utilize the active materials at high mass loading. Here, a 3D printed graded graphene aerogel (3D GA) that contains sparsely separated exterior ligaments is developed to create large open channels for mass transport as well as densely arranged interior ligaments providing large ion-accessible active surface. The unique structural design homogenizes the thickness of electro deposited MnO 2 even at an ultrahigh mass loading of ≈70 mg cm -2 . The electrode achieves a remarkable volumetric capacity of 29.1 mA h cm -3 in the non-aqueous electrolyte. A Li-ion hybrid capacitor device assembled with a graded 3D GA/MnO2 cathode and graded 3D GA/VO x anode exhibits a wide voltage window of 0–4 V and a superior volumetric energy density of 20.2 W h L -1 . The findings offer guidance on 3D printed electrode design for supporting ultrahigh loading of active materials and developments of high energy density energy storage devices.

electrochemical energy storage↗

Nonlinear Conductivities and Electrochemical Performances of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Electrodes

There is increasing research attention on optimizing the carbon black nanoparticles’ structure and loading procedure for improving conductivities and thus, electrochemical performances of cathodes in lithium-ion batteries. Recently, LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523) has been actively investigated due to its larger specific capacity and lower cost compared to conventional cathode materials. Presented here is a high energy density NCM523 cathode obtained by reducing the carbon content using the state-of-the-art carbon nanoparticles developed at Cabot Corporation. It is the first time that the nonlinear conductivity of NCM523 electrodes has been discovered, which is significantly impacted by the dispersion and surface crystalline quality of carbon black nanoparticles, especially when the loading of carbon black is only 1 wt%. The nonlinear conductivity of the cathodes can dramatically affect their electrochemical performances at high rates ($\geqq$3C), which is close to the tunneling saturated current. In addition, there is no discernable difference in terms of the rate and cycle performance of the NCM523 electrodes, when reducing the loading of novel carbon black nanoparticles from 5 wt% to 1 wt% in the cathode. Therefore, the energy density of the electrode can be increased by 9% by using existing commercially available electrode materials.

25 ENERGY STORAGE↗

Pinned Electrode/Electrolyte Interphase and Its Formation Origin for Sulfurized Polyacrylonitrile Cathode in Stable Lithium Batteries

Sulfurized polyacrylonitrile (SPAN) represents one of the most promising directions for high-energy-density lithium (Li)-sulfur batteries. However, the practical application of Li||SPAN is currently limited by the insufficient chemical/electrochemical stability of electrode/electrolyte interphase (EEI). Here, a pinned EEI layer is designed for stabilizing a SPAN cathode by regulating the EEI formation mechanism in an advanced LiFSI/ether/fluorinated-ether electrolyte. Computational simulations and experimental investigations reveal that, benefiting from the nonsolvating nature, the fluorinated-ether can not only act as a protective shield to prevent the Li polysulfides dissolution but also, more importantly, endow a diffusion-controlled EEI formation process. It promotes the formation of a uniform, protective, and conductive EEI layer pinning into SPAN surface region, enabling the high loading Li||SPAN batteries with superior cycling stability, wide temperature performance, and high-rate capability. Finally, this design strategy opens an avenue for exploring advanced electrolytes for Li||SPAN batteries and guides the interface design for broad types of battery systems.

25 ENERGY STORAGE↗

Investigation of the flickering of La{sub 2}O{sub 3} and ThO{sub 2} doped tungsten cathodes

Short-arc lamps are equipped with tungsten electrodes due to their ability to withstand a high thermal load during operation. Nominal currents of more than one hundred amperes lead to a cathode tip temperature near the melting point of tungsten. To reduce the electrode temperature and, thereby, to increase the maintenance of such lamps, ThO{sub 2} or tentatively La{sub 2}O{sub 3} are added to the electrode material. They generate a reduced work function by establishing a monolayer of emitter atoms on the tungsten surface. Emitter enrichments on the lateral surface of doped cathodes are formed. They are traced back to transport mechanisms of emitter oxides in the interior of the electrode and on the electrode surface in dependence of the electrode temperature and to the redeposition of vaporized and ionized emitter atoms onto the cathode tip by the electric field in front. The investigation is undertaken by means of glow discharge mass spectrometry, scanning electron microscope images, energy dispersive x-ray spectroscopy, and through measurements of the optical surface emissivity. The effect of emitter enrichments on the stability of the arc attachment is presented by means of temporally resolved electrode temperature measurements and by measurements of the luminous flux from the cathode-near plasma. They show that the emitter enrichments on the lateral surface of the cathode are attractive for the arc attachment if the emitter at the cathode tip is depleted. In this case, it moves along the lateral surface from the cathode tip to sections of the cathode with a reduced work function. It induces a temporary variation of the cathode tip temperature and of the light intensity from the cathode-near plasma, a so-called flickering. In particular, in case of lanthanated cathodes, strong flickering is observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of Applied Stress on Atmospheric Corrosion and Pitting Characteristics in 304L Stainless Steel

For this study, the effects of applied stress, ranging from tensile to compressive, on the atmospheric pitting corrosion behavior of 304L stainless steel (SS304L) were analyzed through accelerated atmospheric laboratory exposures and microelectrochemical cell analysis. After exposing the lateral surface of a SS304L four-point bend specimen to artificial seawater at 50°C and 35% relative humidity for 50 d, pitting characteristics were determined using optical profilometry and scanning electron microscopy. The SS304L microstructure was analyzed using electron backscatter diffraction. Additionally, localized electrochemical measurements were performed on a similar, unexposed, SS304L four-point bend bar to determine the effects of applied stress on corrosion susceptibility. Under the applied loads and the environment tested, the observed pitting characteristics showed no correlation with the applied stress (from 250 MPa to -250 MPa). Pitting depth, surface area, roundness, and distribution were found to be independent of location on the sample or applied stress. The lack of correlation between pitting statistics and applied stress was more likely due to the aggressive exposure environment, with a sea salt loading of 4 g/m 2 chloride. The pitting characteristics observed were instead governed by the available cathode current and salt distribution, which are a function of sea salt loading, as well as pre-existing underlying microstructure. In microelectrochemical cell experiments performed in Cl - environments comparable to the atmospheric exposure and in environments containing orders of magnitude lower Cl - concentrations, effects of the applied stress on corrosion susceptibility were only apparent in open-circuit potential in low Cl - concentration solutions. Cl - concentration governed the current density and transpassive dissolution potential.

36 MATERIALS SCIENCE↗

Tailoring electrode microstructure via ink content to enable improved rated power performance for platinum cobalt/high surface area carbon based polymer electrolyte fuel cells

Improvements in polymer electrolyte fuel cell (PEFC) electrode performance have primarily focused on catalyst and ionomer developments, marginalizing the importance of catalyst ink formulation. In this study, the effect of ink formulation is examined across a series of cathodes comprised of PtCo supported on high surface area carbon (PtCo/ HSC ) and Nafion ionomer using an array of in situ electrochemical and ex situ characterization techniques. In contrast to prior work on Pt/Vu systems, ink water content had little effect on the electrochemically determined ionomer coverage for the PtCo/HSC electrocatalyst examined here. Characterization using nano-scale resolution X-ray computed tomography (nano-CT) demonstrated that water-rich ink formulations lead to a reduction in aggregate size (ionomer + PtCo/HSC), improving local O 2 transport. This understanding, combined with the use of a commercially-available electrocatalyst was used to produced state-of-the-art membrane electrode assemblies with Pt loadings of 0.03/0.08 mg Pt /cm 2 on the anode and cathode respectively, having; i) > 1 A/mg Pt (0.9 V iR-free , 150 kPa, 80 °C, 100% RH, H 2 /O 2 ), ii) 320 mA/cm 2 at 0.8 V, 150 kPa, 80 ° C, 100% RH, H 2 /Air), and iii) > 1 W/cm 2 elec at rated power (0.67 V, 250 kPa, 94 °C, 65% RH, H 2 /Air) or < 0.11 g Pt /kW rated .

25 ENERGY STORAGE↗

High protonic resistance of hydrocarbon-based cathodes in PEM fuel cells under low humidity conditions: Origin, implication, and mitigation

Hydrocarbon-based electrodes for proton-exchange membrane fuel cells face challenges in closing the performance gap with electrodes based on perfluorosulfonic acid ionomers, particularly under low humidity conditions. Alongside increased oxygen transport resistance and higher kinetic-induced overpotentials, the protonic resistance of these fluorine-free electrodes is the primary hurdle to improved performance. This study systematically investigates the origin and impact of the cathode protonic resistance on fuel cell performance, utilizing sulfonated phenylated polyphenylenes as hydrocarbon ionomers. Electrochemical characterization at low relative humidity (≤50 %) reveal a high protonic resistance arising from both lower conductivity of the hydrocarbon thin film compared to the bulk membrane and increased cathode tortuosity at a gas transport-optimized ionomer to carbon (I/C) ratio of 0.2. The poor protonic resistance at low relative humidities leads to a non-homogeneous current distribution across the thickness of the cathode electrode, resulting in lower catalyst utilization. To address this issue, reducing the thickness of the cathode CL while maintaining a constant Pt loading (i.e., increasing the Pt on carbon ratio) significantly reduces protonic resistance. This improvement compensates for the kinetic disadvantages of highly loaded carbon particles and results in a considerable performance increase by 40 % at 0.75 V under low relative humidities.

25 ENERGY STORAGE↗