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At least 163 records · Page 9

Enhancing Li + Transport in NMC811||Graphite Lithium–Ion Batteries at Low Temperatures by Using Low–Polarity–Solvent Electrolytes

LiNi x Co y MnzO 2 (x+y+z=1)||graphite lithium-ion battery (LIB) chemistry promises practical applications. However, its low-temperature (≤ –20°C) performance is poor because the increased resistance encountered by Li + transport in and across the bulk electrolytes and the electrolyte/electrode interphases induces capacity loss and battery failures. Though tremendous efforts have been made, there is still no effective way to reduce the charge transfer resistance (R ct ) which dominates low-temperature LIBs performance. In this work, we propose a strategy of using low-polarity-solvent electrolytes which have weak interactions between the solvents and the Li + to reduce R ct , achieving facile Li + transport at sub-zero temperatures. The exemplary electrolyte enables LiNi 0.8 Mn 0.1 Co 0.1 O 2 ||graphite cells to deliver a capacity of ≈113 mAh g –1 (98% full-cell capacity) at 25°C and to remain 82% of their room-temperature capacity at –20°C without lithium plating at 1/3C. They also retain 84% of their capacity at –30°C and 78% of their capacity at –40°C and show stable cycling at 50°C.

25 ENERGY STORAGE↗

Thermally Aged Li–Mn–O Cathode with Stabilized Hybrid Cation and Anion Redox

Though low-cost and environmentally friendly, Li–Mn–O cathodes suffer from low energy density. Although synthesized Li 4 Mn 5 O 12 -like overlithiated spinel cathode with reversible hybrid anion- and cation-redox (HACR) activities has a high initial capacity, it degrades rapidly due to oxygen loss and side-reaction-induced electrolyte decomposition. In this study, we develop a two-step heat treatment to promote local decomposition as Li 4 Mn 5 O 12 → 2LiMn 2 O 4 + Li 2 MnO 3 + 1/2 O 2 ↑, which releases near-surface reactive oxygen that is harmful to cycling stability. The produced nanocomposite delivers a high discharge capacity of 225 mAh/g and energy density of over 700 Wh/kg at active-material level at a current density of 100 mA/g between 1.8 to 4.7 V. Benefiting from suppressed oxygen loss and side reactions, 80% capacity retention is achieved after 214 cycles in half cells. With industrially acceptable electrolyte amount (6 g/Ah), full cells paired with Li 4 Ti 5 O 12 anode have a good retention over 100 cycles.

25 ENERGY STORAGE↗

Stabilizing a Li–Mn–O Cathode by Blocking Lattice O Migration through a Nanoscale Phase Complex

Among all intercalation cathodes for Li-ion batteries, Li–Mn–O layered oxides offer the highest initial energy density at the lowest cost, due to the joint contribution from cationic and anionic redox chemistry. However, the poor cycling capability, resulting from the continuous lattice O loss at high potentials (>4.5 V), hinders practical applications. Herein, we employed phase complex engineering to obtain a new Li–Mn–O nanohybrid cathode featuring the uniform and coherent integration of layered nanodomains and spinel nanodomains. The combination of DFT calculations, synchrotron-based transmission X-ray microscopy, in situ differential electrochemical mass spectrometry, in situ synchrotron XRD, and electrochemical tests demonstrated that the O migration path in layered nanodomains was blocked by the neighboring spinel nanodomains with a higher oxygen vacancy migration energy, thus effectively suppressing the irreversible lattice O loss at high potentials and enhancing the cycling stability in both capacity and average voltage. Finally, the strategy is experimentally demonstrated to be effective and it leads to a new path for developing stable high-energy-density cathode materials.

25 ENERGY STORAGE↗

Fluorination-Enhanced Surface Stability of Cation-Disordered Rocksalt Cathodes for Li-Ion Batteries

Cation-disordered rocksalt (DRX) materials have emerged as a class of novel high-capacity cathodes for Li-ion batteries. However, commercialization of DRX cathodes will require reducing their capacity decay, which has been associated with oxygen loss during cycling. Recent studies have shown that fluorination of DRX cathodes can effectively reduce the oxygen loss and improve the cycling stability; however, the underlying atomic-scale mechanisms remain elusive. Herein, using a combination of electrochemical measurements, scanning transmission electron microscopy, and electron energy loss spectroscopy, we examine the correlation between the electrochemical properties and structural evolution in Mn-redox-based DRX cathodes, Li1.2Ti0.4-xMn0.4+xO2.0-xFx (x = 0 and 0.2). We find that fluorination strongly suppresses structural amorphization and void formation initiated from the particle surface, therefore greatly enhancing the cyclability of the cathode. We further reveal a novel rocksalt-to-spinel-like structural transformation in the DRX bulk, which surprisingly contributes to a gradual capacity increase during cycling. Our results provide important insight for the design of novel DRX cathodes with high capacity and long cycle life.

Li, Linze↗

Prelithiated SiO x /Graphite-NMC811 Cells: Capacity Loss, Impedance Rise and Hidden Degradation Pathways Revealed Using Three-Electrode Diagnostics

Electrodes containing SiO x /graphite (Gr) materials are attractive as anodes for high-energy lithium-ion batteries. However, their mechanical deformation, electrochemical response, and impedance evolution during long-term cycling are strongly coupled, complicating accurate diagnosis of performance fade mechanisms. In this work, the behavior of electrochemically prelithiated SiO x /Gr anodes paired with NMC811 cathodes is systematically investigated using techniques that include in-situ dilatometry, three-electrode electrochemistry, and multiscale post-cycling microscopy. The SiO x /Gr electrode exhibits a maximum expansion of 49% upon lithiation to 10 mV vs Li + /Li, with 84% of the expansion and 91% of the capacity being reversible. In full cells, relatively stable cycling with only 12% capacity fade over 500 cycles is observed. Three-electrode experiments reveal cell-level impedance growth, which is dominated by the NMC811 cathode: the SiO x /Gr anode exhibits minimal net impedance rise and an initial impedance decrease at low potentials. Despite this apparent electrochemical stability, cross-sectional SEM, PFIB tomography, and cryo-STEM reveal irreversible anode thickening caused by the accumulation of an inorganic-rich solid electrolyte interphase (SEI) permeating the anode bulk. Electrode potential-shift analysis further demonstrates that Li + ions released from lithium reservoirs in the prelithiated anode mask true lithium inventory loss during aging. These results demonstrate that low-expansion SiO x /Gr anodes can simultaneously exhibit favorable cycling and impedance metrics while undergoing substantial, hidden degradation, underscoring the importance of electrode-resolved diagnostics for evaluating prelithiated silicon-based anodes.

25 ENERGY STORAGE↗

Engineering metal-oxide interface by depositing ZrO 2 overcoating on Ni/Al 2 O 3 for dry reforming of methane

Zirconium oxide (ZrO 2 ) was deposited onto Ni/Al 2 O 3 catalyst as overcoating by atomic layer deposition (ALD) for dry reforming of methane (DRM). High-temperature heating during H-2-reduction could transform the ALD-prepared ZrO 2 thin film to tetragonal phase and crack the encapsulating layer on Ni sites, which constructed a beneficial Ni-ZrO x interface. Here, interfacial surface oxygen vacancies on ZrO 2 overcoating were induced by the partial reduction of ZrO 2 surface during high-temperature H 2 reduction, with the assistance of Ni. During DRM, the interfacial oxygen vacancies enhanced CO 2 activation by dissociating CO 2 and releasing active O, thereby limiting carbon formation. For DRM at 700 °C and 800 °C, Ni/Al 2 O 3 with 5 cycles of ZrO 2 ALD overcoating enhanced both activity and stability significantly. For a 100-h DRM test at 600 °C, no deactivation was observed for the Ni/Al 2 O 3 catalyst with 10 cycles of ZrO 2 ALD overcoating, as compared to 59% relative activity loss of Ni/Al 2 O 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating sealability of blended smart polymer and fiber additive for geothermal drilling with the effect of fracture opening size

Geothermal formations often contain extensive fracture networks. These fracture networks contribute to the significant loss of drilling fluids during geothermal drilling. Multiple loss circulation materials (LCM) such as fiber, granules, and pills have been proposed to tackle this problem but with only limited success. Recent advances in materials science have led to the development of thermoset shape memory polymers (SMP) to address the lost circulation problem. In this paper, we evaluate a thermoset SMP performance in sealing near wellbore fractures of different sizes in geothermal wells. The SMP performance was assessed using granite disks and cylindrical granite cores having fracture sizes of 1000 μm and 3000 μm. A static filtration test was performed using cedar fiber, CaCO 3 , and SMP. Results showed cedar fiber performed better than the CaCO 3 ., reducing fluid loss by 89% and improving sealing pressure by 200 psi. A novel dynamic testing unit that allows for high-temperature testing under flowing conditions was used in this study. The analysis showed that 3% by weight SMP and fiber blends could bridge and plug the 1000 μm fracture. For a larger fracture of 3000 μm width, there was a need to increase the weight concentration of the SMP to 6% to plug the fracture opening effectively. We showed the influence of key parameters such as the type of LCM, concentration, and particle size distribution in optimizing the performance of drilling fluid loss treatment.

02 PETROLEUM↗

Realistic Ion Dynamics through Charge Renormalization in Nonaqueous Electrolytes

While many practically important electrolytes contain lithium ions, interactions of these ions are particularly difficult to probe experimentally because of their small X-ray and neutron scattering cross sections and large neutron absorption cross sections. Molecular dynamics (MD) is a powerful tool for understanding the properties of nonaqueous electrolyte solutions from the atomic level, but the accuracy of this computational method crucially depends on the physics built into the classical force field. In this study, we demonstrate that several force fields for lithium bistriflimide (LiTFSI) in acetonitrile yield a solution structure that is consistent with the neutron scattering experiments, yet these models produce dramatically different ion dynamics in solution. Such glaring discrepancies indicate that inadequate representation of long-range interactions leads to excessive ionic association and ion-pair clustering. We show that reasonable agreement with the experimental observations can be achieved by renormalization of the ion charges using a “titration” method suggested herewith. This simple modification produces realistic concentration dependencies for ionic diffusion and conductivity in <2 M solutions, without loss in quality for simulation of the structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Titanium Nitride as an Intermetallic Diffusion Barrier for Hydrogen Permeation in Palladium–Vanadium Composite Membranes

Hydrogen purification is a critical industrial process, and there are ongoing efforts to develop low-cost alternatives to palladium foil membranes. Titanium nitride (TiN) is studied as an interdiffusion barrier to enable hydrogen permeation in composite palladium–vanadium membranes. TiN was deposited via reactive sputtering, and films with the desired (200) orientation were obtained in the metallic regime at 400 °C under a 200 V bias to the substrate. The permeability of thin-film TiN was determined with palladium-based sandwich structures. TiN layers up to 10 nm resulted in a minimal decrease in flux (~20%) relative to a freestanding PdCu foil, which was attributed to the interfacial resistance. At greater thicknesses, the TiN layer was rate-limiting, and it was found that the effective permeability of the sputtered TiN thin films was ~6 × 10−12 mol s−1 m−1 Pa−0.5. Composite Pd|TiN|V|TiN|Pd membranes exhibited permeability values up to three times greater than pure palladium, exhibiting stability at 450 °C for over 100 h, with the lack of intermetallic diffusion and alloy formation being confirmed with XRD. The membranes were unstable at 500 °C, which was attributed to the instability of the thin Pd layer and loss of catalytic activity.

Biochemistry & Molecular Biology↗

Three-Dimensional Polymeric-Scaffold-Based Current Collector for a Lithium Metal Anode toward High-Energy-Density Batteries

Here, the practical applications of high-energy-density rechargeable lithium (Li) metal batteries (LMBs) have been impeded by the intrinsic issues of the Li metal anode (LMA) including high reactivity with electrolyte and dendritic formation. Conventional LMAs, which have the "hostless" feature consisting of a Li layer on a two-dimensional copper (Cu) foil as a current collector, led to additional loss in specific energy density, since Cu is a nonfaradaic heavy metal, bringing formidable areal capacity loss. To address these problems, a heat-treated three-dimensional-structured Cu-coated polyimide (HT-Cu@PI) membrane is designed and fabricated as a current collector. Benefiting from this unique material/structure, it enables not only better electrochemically deposited Li by a uniform/continuous Li-ion transport pathway but also a significant increase in the gravimetric/volumetric energy densities of LMBs by allowing more Li deposition in a fixed weight/volume. Therefore, this new LMA structure will accelerate the practical application of high-energy-density LMBs.

25 ENERGY STORAGE↗

Simulation of triggering and evolution of ELM by pellet injection in EAST under BOUT++ framework

A BOUT ++ three-field magnetohydrodynamic model is employed to study the triggering and evolution of edge localized mode (ELM) by Li pellets injected along the outer mid-plane in the EAST configuration. The linear simulation shows that compared with a large deposition on the pedestal top (scenario I), a smaller deposition within the steep-gradient pedestal region (scenario II) can stimulate much larger linear growth rates of all-n peeling-ballooning modes (PBMs). The nonlinear simulation shows that there exists a pellet size threshold for ELM triggering for two deposition locations; the threshold for scenario I predicted in the present study matches the EAST observation well. Comparison of the two scenarios reveals that a smaller deposition is sufficient to trigger an ELM in a much shorter time in scenario II, whose ELM size is comparable to that in scenario I. This conclusion confirms previous DIII-D and ASDEX-Upgrade observations, suggesting that the steep-gradient pedestal region is a favorable deposition location for ELM triggering with minimum pellet size. Simulation analyses also find that the positive radial gradient of the hump-like pressure profile in the outer mid-plane induced by the pellet deposition plays a different role in the two scenarios. In scenario I, the force resulting from the gradient hinders the outflow of core plasmas and in return, the perturbation is suppressed from spreading inwards after ELM crashes. In scenario II, with a sizable deposition, the gradient results in another competitive perturbation growth region during the linear phase, thus dispersing the free energy and reducing the efficiency of destabilizing PBMs by pellet injection. The suppressing effect of saturated zonal flow on other modes, the short ELM fast crash phase, and the restricting transport effect of the positive radial pressure gradient work together to constrain the pedestal energy loss, especially when the pellet deposition amount is high.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Incorporating Valve Switching Losses Into a Static Optimal Control Algorithm for the Hybrid Hydraulic-Electric Architecture (HHEA)

The Hybrid Hydraulic-Electric Architecture (HHEA) has, in recent years, been proposed as an energy efficient alternative to conventional load-sensing architectures in mobile machines such as excavators and wheel-loaders. HHEA leverages the advantages of hydraulic power and electric power to eliminate throttling valves while also improving the energy and control performance of the system. The architecture utilizes a set of common pressure rails to provide a majority of power and and a small electric motor driven pump to modulate this power to meet the exact demand. Previous work has developed a computationally efficient Lagrange Multiplier approach for determining the optimal pressure rail selections that minimizes the energy losses in the system. The static model used considers only the energy use for each pressure rail selection but not the losses associated with the valves during the transition. This paper presents an approach to include the switching losses in the model and in the optimization procedure. To capture the switching losses, switching events between different rails and at various input and output flow rates were simulated with consideration of valve spool dynamics. A parameterized model that summarizes the losses is then obtained, allowing switching losses to be added to the previous energy analysis. The performance of the switching loss model was compared with reference data obtained from a high-fidelity simulation model. To incorporate the switching losses into optimal control algorithm, an efficient dynamic programming approach that prevents frequent switching is adopted in place of the Lagrange multiplier approach. The overall effect of switching losses on the energy consumption and optimal control decisions is presented. In general, switching losses contribute to about 9–10% of input energy.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Investigation of Chemical Species in the Corrosion Barrier Layer on Thermal CO 2 Treated AZ91D Magnesium Alloy with Lithium Nitrate

A unique corrosion barrier layer, formed by thermal CO 2 treatment with LiNO 3 on AZ91D, was characterized to reveal the chemical species and their spatial distribution using the combination of scanning transmission electron microscopy (STEM), energy dispersive spectroscopy (EDS), and electron energy loss spectroscopy (EELS) techniques. Two distinct and spatially segregated phases were identified as Li compound(s) with MgCO 3 and MgO in the surface barrier layer. Finally, based on the characterization results, it is presumed that the reaction of Mg oxide/hydroxide with LiNO 3 and CO 2 occurred preferentially in some local areas where Li compound(s) with MgCO 3 were present, but the unreacted areas contained MgO in the surface barrier layer.

36 MATERIALS SCIENCE↗

Size-Selective Nanoporous Atomically Thin Graphene Separators for Lithium–Sulfur Batteries

Lithium–sulfur batteries (LSBs) are extensively researched for their high energy densities but are hindered by the lithium polysulfide (LiPS) shuttling effect, which results in poor cyclability. A popular mitigation strategy is separator modification, where a LiPS trapping material is slurry-coated onto a conventional microporous polypropylene (PP) separator. This additional mass and volume unfortunately compromise the overall energy density of the LSB. This study aims to take a separator modification approach that avoids this issue. Nanoporous atomically thin membranes (NATMs) made of graphene are gaining attention for their scalable synthesis, tunable pore size, and negligible pore length. Herein, we apply a well-characterized graphene NATM for reasons similar to those of a size-selective interlayer in LSBs. The tailored pore size of ∼0.7–1.0 nm and atomic thinness facilitate the passage of Li + (solvated ionic diameters ∼0.54–1.26 nm) and blockage of larger LiPS (solvated ionic diameters ∼0.81–1.69 nm) without adding significant impedances or mass. The sulfur confinement is confirmed through scanning electron microscopy and energy-dispersive X-ray spectroscopy elemental analysis of the Li anode. An LSB with a NATM@PP separator shows virtually no capacity loss over 150 cycles, demonstrating efficacy of size-selective molecular sieving using NATMs in LSBs.

battery separator↗

Diffusion and Deformation Mechanism Maps in Li Metal from Atomistic Simulations

The rate of Li transport in the Li metal anode is important for the operation of Li metal-solid state batteries. Here, transport rates due to diffusion and creep are predicted in Li using atomistic simulations. First, molecular dynamics is used to estimate the rate of Li diffusion along dislocations and in grain boundary triple junctions. By combining this data with that from a prior study of grain boundary diffusion the dominant mechanisms and rates of self-diffusion in Li polycrystals are predicted as a function of grain size, grain shape, dislocation density, and temperature. Second, the dominant creep mechanisms are predicted and used to estimate critical current densities and void annihilation times. Grain boundary sliding and coble creep are the dominant mechanisms for micron-sized grains. Lastly, a continuum model for interfacial contact loss reveals that high dislocation densities of ∼10 12 /cm 2 enable achieving battery performance targets for Li grain sizes of ∼10 μm.

Batteries↗

Modeling Lithium Diffusion in Battery Cathodes Considering Chemo-Mechanically Induced Damage

This talk will present a 3D, continuum-level damage model for simulating Lithium diffusion within generated Li_{x}Ni_{0.5}Mn_{0.3}Co_{0.2} (NMC 532) secondary cathode particles. The primary motivation of the particle-level model is to inform cathode-particle design and determine charging profiles that reduce cathode fracture. The model considers NMC 532 secondary particles containing an agglomeration of anisotropic, randomly oriented grains. The model predicts that secondary-particle fracture is primarily due to non-ideal grain interactions with slight dependence on high-rate charge demands. The model predicts that small secondary-particles with large grains develop significantly less damage than larger secondary particles with small grains. Finally, the model predicts most of the chemo-mechanical damage accumulates in the first high-rate cycles. This chemo-mechanical “damage saturation” effect indicates that initial secondary-particle fracture occurs within the first few cycles, while long-term cathode degradation is not solely chemo-mechanically induced.

47 OTHER INSTRUMENTATION↗

Extended Interfacial Stability through Simple Acid Rinsing in a Li-Rich Oxide Cathode Material

Layered Li-rich Ni, Mn, Co (NMC) oxide cathodes in Li-ion batteries provide high specific capacities (>250 mAh/g) via O-redox at high voltages. However, associated high-voltage interfacial degradation processes require strategies for effective electrode surface passivation. Here, we show that an acidic surface treatment of a Li-rich NMC layered oxide cathode material leads to a substantial suppression of CO 2 and O 2 evolution, ~90% and ~100% respectively, during the first charge up to 4.8 V vs. Li +/0 . CO 2 suppression is related to Li 2 CO 3 removal as well as effective surface passivation against electrolyte degradation. This treatment does not result in any loss of discharge capacity and provides superior long-term cycling and rate performance compared to as-received, untreated materials. We also quantify the extent of lattice oxygen participation in charge compensation (“O-redox”) during Li + removal by a novel ex-situ acid titration. Our results indicate that the peroxo-like species resulting from O-redox originate on the surface at least 300 mV earlier than the activation plateau region around 4.5 V. X-ray photoelectron spectra and Mn -L X-ray absorption spectra of the cathode powders reveal a Li + deficiency and a partial reduction of Mn ions on the surface of the acid-treated material. More interestingly, although the irreversible oxygen evolution is greatly suppressed through the surface treatment, our O K-edge resonant inelastic X-ray scattering shows the lattice O-redox behavior largely sustained. The acidic treatment, therefore, only optimizes the surface of the Li-rich material and almost eliminates the irreversible gas evolution, leading to improved cycling and rate performance. This work therefore presents a simple yet effective approach to passivate cathode surfaces against interfacial instabilities during high-voltage battery operation.

25 ENERGY STORAGE↗

Quantitative insights for diagnosing performance bottlenecks in lithium–sulfur batteries

Lithium–sulfur (Li–S) batteries hold significant promise for electric vehicles and aviation due to their high energy density and cost-effectiveness. However, understanding the root causes of performance degradation remains a formidable challenge, as the interplay of multiple factors obscures key failure mechanisms. A major limitation has been the inability to quantify soluble sulfur species within practical detection limits accurately and to correlate electrochemical processes with associated physical inventory changes. Here, we introduce the high-performance liquid chromatography-ultraviolet spectroscopy and gas chromatography sequential characterization (HUGS) toolkit, capable of precisely quantifying seven distinct sulfur and polysulfide species at concentrations as low as 40 ppb. HUGS has been successfully applied to practical coin and pouch cells without requiring cell modification. Furthermore, our self-developed software, Dr HUGS, enhanced the data analysis speed by over 30 times, enabling multi-source data integration and delivering comprehensive analysis results within minutes. Using HUGS, we identify significant capacity losses from inactive lithium and sulfur during initial cycles and sulfide-rich solid–electrolyte interphase (SEI) formation on the anode during later cycles. Notably, our findings reveal that soluble polysulfides have minimal contributions to capacity loss, challenging long-standing assumptions. Moreover, HUGS demonstrates that constant-pressure setups in Li–S pouch cells improve compositional uniformity compared to constant-gap configurations. For sulfurized polyacrylonitrile (SPAN) cathodes, unique issues such as non-sulfide SEI formation and lithium pulverization are observed, which can be mitigated through localized high-concentration electrolytes to enhance lithium inventory retention. By enabling precise quantification of critical inventory components, HUGS provides transformative insights into failure mechanisms across various electrolytes and cathode chemistries, guiding rational design strategies for next-generation energy storage systems.

25 ENERGY STORAGE↗