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At least 91 records · Page 5

An efficient construction of nano-interfaces for excellent coking tolerance of cermet anodes

Solid oxide fuel cells (SOFCs) are promising energy conversion devices for the effective and convenient utilization of hydrocarbons (for example, methane) to electricity. However, the development of direct methane SOFCs is primarily hindered by the poor coking tolerance of the state-of-the-art Ni-based cermet anodes. Herein, we efficiently construct nano-interfaces in the anode by infiltrating a Ni 0.6 Y 0.064 Zr 0.336 O 2-δ (NYZ) catalyst onto the traditional Ni-based cermet anode to effectively enhance the coking tolerance. After being reduced in H 2 , Ni and Y 0.16 Zr 0.84 O 2-δ (YSZ) nanoparticles (NPs) are in situ formed on the surface of the Ni-YSZ substrate. The roughened anode demonstrates significantly improved fuel oxidation activity and coking tolerance, due likely to the formation of nano-interfaces. Specifically, when applied in the Ni-YSZ-based anode-supported SOFCs, a high peak power density of 1.785 W cm –2 and a stable operation of ~ 240 h with no observable degradation is achieved at 750 °C in nearly dry methane (3% H 2 O). Finally, a density functional theory study suggests that the excellent coking tolerance is attributed to the formation of OH species on Ni/YSZ nano-interfaces, which would further interact with intermediate carbon species to generate COH intermediates.

30 DIRECT ENERGY CONVERSION↗

User chooses coating properties

Anodizing technique allows independent selection of coating thermal emittance and solar absorption. Process has three phases: initial material processing, which prepares material and establishes initial values of emittance and absorption; anodizing with chromic acid solution, which determines final values; and material postprocessing. Stability tests show less than 15 percent coating degradation over 2,000 hour solar exposure.

Gilliland, C. S.↗

Controlled lithium stripping enables a stable interface for long-cycling anode-free solid-state batteries

Anode-free solid-state batteries (AFSSBs) are a promising route toward achieving high energy density. In these cells, the anode contains no pre-stored lithium (Li). Instead, the entire Li inventory originates from the cathode and is freshly deposited onto a bare current collector during charging. However, achieving uniform and defect-free Li plating on this bare current collector remains a major challenge, often resulting in low Li plating/stripping efficiency and rapid capacity decay. Here, for the first time, operando neutron imaging is employed to visualize Li plating/stripping behavior in an anode-free full cell with LiNi0.82Mn0.07Co0.11O2 (NMC) as the cathode. Operando measurements reveal that complete stripping of Li leaves isolated Li residues on the current collector, which degrades the interfacial contact between the current collector and the solid-state electrolyte. To mitigate this interfacial issue and promote more uniform Li deposition, we implement a discharge-cutoff-voltage strategy that intentionally retains a thin residual Li layer after stripping. This preserved Li-containing interfacial reservoir not only improves interfacial contact but also serves as an in situ formed seed layer that enables more homogeneous subsequent Li plating. As a result, the optimized anode-free cell with limited stripping depth exhibits excellent long-term cycling stability, maintaining a discharge capacity of 112.1 mAh g−1 with a capacity retention of 80.6% and an average coulombic efficiency of approximately 99.9% after 500 cycles at 0.25 C. In contrast, the cell with a conventional discharge cutoff voltage of 2.8 V exhibits rapid capacity decay, retaining only 59.7 mAh g−1 after 50 cycles with a capacity retention of 40.7%. This work demonstrates that limiting deep stripping to preserve a thin Li-containing interfacial layer can effectively improve the cycling stability of sulfide-based AFSSBs.

Wang, Jiwei [Northeastern University, Boston]↗

Stability of Mn-Doped TiO 2 Thin-Film Anodes during Water Oxidation Reactions

Incorporating manganese atoms into TiO 2 has been shown to improve its activity for water oxidation. However, its activity has been observed to steadily degrade under constant applied potential, especially at more oxidizing applied potentials. Here, the compositional profile and electrochemical stability of Mn-doped TiO 2 (Mn:TiO 2 ) thin-film electrodes precisely fabricated by atomic layer deposition (ALD) were evaluated to elucidate the mechanisms of electrode degradation. Although ALD enables the deposition of Mn dopants throughout the film thickness, only Mn within 1.5 nm of the surface was observed to be redox active. Annealing Mn:TiO 2 films in air leads to the diffusion of Mn toward the electrode surface and oxidation of the Mn and alters the redox behavior. Annealing endows greater stability to Mn redox behavior but does not fully stabilize the water oxidation current, suggesting that the two electrochemical processes are not precisely correlated. In situ inductively coupled plasma mass spectrometry reveals that Mn is lost from Mn:TiO 2 films at potentials greater than 1.8 V vs RHE. However, the initial Mn loss is equivalent to less than a single ALD layer of MnO x . Longer-term constant potential experiments suggest that Mn is lost from up to 1 nm of the electrode surface but that this loss may account for only a portion of the diminished water oxidation activity.

atomic layer deposition↗

A Holistic Stabilization of the Anode in Lithium‐Sulfur Batteries Through a Ternary Alloy Fusion

The anode in lithium–sulfur batteries (LSBs) is plagued by not only inhomogeneous lithium (Li) deposition, but also by parasitic side-reactions. Often, a thick anode (∼400 µm) is used to compensate for these drawbacks, lowering gravimetric and volumetric energy densities. In this work, we demonstrate a ternary alloy anode fabricated via scalable thermal fusion of Li with aluminum (Al) and tellurium (Te) to cohesively address these issues. The Al–Li skeleton serves to homogenize Li deposition as well as reinforce the anode, allowing it to be rolled down to low thicknesses. Te incorporation suppresses the reaction of Li with polysulfides (Li 2 Sn) to form lithium sulfide (Li 2 S) and electrolyte degradation. It can also facilitate the formation of polytellurosulfides (Li 2 Te x Sy), which are far more conducive to Li + -ion diffusion. Even under a lean electrolyte/sulfur (E/S) ratio of 8 µL mg −1 and a low negative/positive (N/P) ratio of 3, capacities over 900 mA h g −1 at a C/5 rate are obtained in cells with Li–Te–Al anodes with a capacity retention of 80% after 70 cycles. In comparison, the baseline lithium-metal anode retains only 35% after 50 cycles. Furthermore, the Li–Te–Al anodes confer a 24% boost to gravimetric energy density at the pouch cell level.

25 ENERGY STORAGE↗

Composite Lithium Metal Structure to Mitigate Pulverization and Enable Long‐Life Batteries

In lithium metal batteries, non‐uniform stripping of lithium results in pit formation, which promotes subsequent non‐uniform, dendritic deposition. This viscous cycle leads to pulverization of lithium which promotes cell shorting or capacity degradation, symptoms further exaggerated by high electrode areal loading and lean electrolytes. Here, to address this challenge, a composite lithium metal anode is engineered that contains uniformly distributed, nanometer‐sized carbon particles. This composite lithium is shown to strip more uniformly since the growth of non‐uniform pits is intercepted by the carbon particles. This mechanism is corroborated by a continuum electrochemical model. Subsequent lithium deposition on carbon particles is also found to be more uniform than on the surface with irregular pits. Notably, the pulverization rate of composite lithium is 26 times slower than that of commercial lithium. Moreover, in a Li‐S battery with sulfurized polyacrylonitrile cathode, the use of the composite anode extends the cycle life by three times when the areal capacity is 8 mAh cm −2 . The approach of using an engineered lithium composite structure to address challenges during both stripping and plating can inform future designs of lithium metal anodes for high areal capacity operations.

high areal capacity↗

Battery detectives: Uncovering cathode impact on anode-free Li cell performance by operando NMR

Here, Anode-free Li-ion batteries could attain new levels of energy density, but challenges remain in controlling deposition and managing degradation. In this issue of Chem, Kwon et al. probe Li metal growth using operando NMR to unravel how cathode materials impact performance and establish criteria for the high-energy/low-cost design tradeoff.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of Degradation and Electrochemical Behavior of Lithium–Oxygen Batteries under Lean Electrolyte Conditions

Lithium-oxygen batteries have garnered much attention in the past decades due to their high energy density and active material abundancy. Decreasing the electrolyte volume is critical to achieving a high energy density for practical applications. Recent works have demonstrated a serious performance limitation at lower electrolyte fillings. Here, in this work, we study specifically the difference between flooded and lean electrolyte lithium-oxygen batteries by systematically tracing the source of performance degradation. We find that the key contributor to the decrease in performance under lean electrolyte conditions stems from the lithium metal anode rather than the cathode. Solid electrolyte interphase (SEI) compositionally appears to be the same from X-ray photoelectron spectroscopy but the coverage is less uniform, and impedance is much higher under lean electrolyte conditions. Such an effect likely produced the observed poorer cycle performance at 10 μL cm -2 (similar to 28% cathode's pore volume filled) vs 100 μL cm -2 (278% of cathode's pore volume) at a capacity of 1.0 mAh cm -2 (0.1 mAh cm -2 ) using an electrolyte composition of 1 M LiTFSI in TEGDME.

Córdoba, Daniel [Argonne National Laboratory (ANL)↗

Cyber-Physical Simulation of an Innovative Solid Oxide Electrolysis Cell - Gas Turbine (SOEC-GT) Hybrid Energy System

To produce green hydrogen at scale and at low cost, the solid oxide electrolysis cell (SOEC) systems would be tied to renewable power sources (mainly solar and wind), leveraging zero-carbon electricity at low prices and even nearly free during overgeneration scenarios. However, due to the intermittency of renewable power generation, the SOEC system is subjected to rapid load transitions that occur not only in diurnal cycles but also in short timeframes (e.g., sub-minute). This can result in fast degradation and thus greatly reduce the SOEC’s lifetime. Our team at the National Energy Technology Laboratory has demonstrated that the anode air flow can have a crucial role in SOEC thermal management. Typically, a higher air flow rate can help to mitigate the local temperature gradient distortion during rapid load transitions. To move a large amount of air, the gas turbine (GT; i.e., compressor-turbine-generator set) has been regarded as the most mature and efficient technology. In this presentation, we show the configuration and preliminary results of an innovative SOEC-GT hybrid energy system in a cyber-physical simulation (CPS) approach.

Zhang, Biao↗

Performance and properties of arsenic passivated lithium-titanium disulfide cells

In order to inhibit chemical degradation associated with the lithium-electrolyte interaction in ambient temperature lithium cells, an attempt was made to synthetically passivate the anode via ion implantation of arsenic. Solvent reduction is reduced although salt reaction with lithium is still present. The performance of the Li-TiS2 cell differs from those with standard electrodes, but further work is necessary to clarify the efficacy of this mode of passivation.

Yen, S. P. S.↗

Tantalum oxide stabilized molybdenum-doped ruthenium oxide electrocatalysts for PEM water electrolysis

Proton exchange membrane (PEM) water electrolysis offers key advantages, including high current density, high efficiency, and compact system architecture for hydrogen production. However, its widespread implementation is limited by the scarcity and high cost of Ir-based anodic catalysts. Herein, we report an Ir-free electrocatalyst for the acidic oxygen evolution reaction (OER): tantalum oxide (TaO x )–coated molybdenum-doped RuO 2 (TaO x -MoRuO 2 ). The catalyst exhibits a low overpotential of 180 mV at 10 mA cm -2 and excellent durability, with a degradation rate of 0.034 mV h -1 over a 150-hour test at 50 mA cm -2 —surpassing other Ru-based catalysts evaluated under similar conditions. A PEM electrolyzer employing TaO x -MoRuO 2 as the anode maintained stable operation for 100 hours at 500 mA cm -2 . In conclusion, the TaO x coating layer suppresses Ru and Mo dissolution, thus enhancing their stability likely via interfacial electronic reconfiguration of Ru and Mo mediated by bridging oxygen atoms.

Durability↗

Lithium Dinitramide as an Additive in Lithium Power Cells

Lithium dinitramide, LiN(NO2)2 has shown promise as an additive to nonaqueous electrolytes in rechargeable and non-rechargeable lithium-ion-based electrochemical power cells. Such non-aqueous electrolytes consist of lithium salts dissolved in mixtures of organic ethers, esters, carbonates, or acetals. The benefits of adding lithium dinitramide (which is also a lithium salt) include lower irreversible loss of capacity on the first charge/discharge cycle, higher cycle life, lower self-discharge, greater flexibility in selection of electrolyte solvents, and greater charge capacity. The need for a suitable electrolyte additive arises as follows: The metallic lithium in the anode of a lithium-ion-based power cell is so highly reactive that in addition to the desired main electrochemical reaction, it engages in side reactions that cause formation of resistive films and dendrites, which degrade performance as quantified in terms of charge capacity, cycle life, shelf life, first-cycle irreversible capacity loss, specific power, and specific energy. The incidence of side reactions can be reduced through the formation of a solid-electrolyte interface (SEI) a thin film that prevents direct contact between the lithium anode material and the electrolyte. Ideally, an SEI should chemically protect the anode and the electrolyte from each other while exhibiting high conductivity for lithium ions and little or no conductivity for electrons. A suitable additive can act as an SEI promoter. Heretofore, most SEI promotion was thought to derive from organic molecules in electrolyte solutions. In contrast, lithium dinitramide is inorganic. Dinitramide compounds are known as oxidizers in rocket-fuel chemistry and until now, were not known as SEI promoters in battery chemistry. Although the exact reason for the improvement afforded by the addition of lithium dinitramide is not clear, it has been hypothesized that lithium dinitramide competes with other electrolyte constituents to react with lithium on the surface of the anode to form a beneficial SEI. Apparently, nitrides and oxides that result from reduction of lithium dinitramide on the anode produce a thin, robust SEI different from the SEIs formed from organic SEI promoters. The SEI formed from lithium dinitramide is more electronically insulating than is the film formed in the presence of an otherwise identical electrolyte that does not include lithium dinitramide. SEI promotion with lithium dinitramide is useful in batteries with metallic lithium and lithium alloy anodes.

Gorkovenko, Alexander A.↗

Lithium-Ion Batteries with Lithium Manganese Iron Phosphate Cathodes and Lithium Titanate Anodes: Linking Electrode Dynamics to Cell Performance

This study examines the electrochemical performance, impedance behavior, and aging mechanisms of lithium-ion cells pairing lithium manganese iron phosphate (LiMn 0.6 Fe 0.4 PO 4 , LMFP64) cathodes with lithium titanate (Li 4 Ti 5 O 12 , LTO) anodes. LMFP64 half-cells display distinct Fe and Mn redox plateaus at ∼3.5 and ∼4.1 V, respectively, and deliver excellent rate capability. Three-electrode measurements show that LMFP64 dominates cell impedance, which changes sharply across the Fe–Mn redox transition and decreases with increasing temperature (30 °C–50 °C). Voltage hysteresis arises mainly from the cathode, with higher C-rates shortening redox plateaus and broadening the transition region. Elevated temperature lowers impedance, especially near the Mn-redox and transition regions, but accelerates capacity fade. Post-cycling analyses of electrodes confirm structural stability of LMFP64 and indicate loss of lithium inventory (LLI) as the source of capacity fade. This LLI causes potential slippage between the LMFP64 and LTO electrodes, which decreases the Fe-redox plateau width. Long-term cycling highlights the critical role of electrode overhang: cathode overhang mitigates capacity fade by buffering lithium loss, whereas anode overhang cells experience faster capacity decline due to uncompensated lithium depletion. These results clarify LMFP64/LTO battery impedance evolution, thermal effects, and degradation pathways and provide insights for their applications in electric vehicles.

Area Specific Impedance↗

Accelerating Corrosion in Solar-Cell Tests

In simple electrochemical cell, two silicon solar cells serve as anode and cathode, respectively. Electrolytic medium and voltage between them accelerate corrosion and migration interactions between cell metal contacts and plastic encapsulant. Degradation of metal contacts becomes evident in few hours. Although developed specifically for cells with Ti/Pd/Ag contacts, technique readily adapted to other metal combinations.

Shalaby, H. M.↗

In Situ Li Seed Formation Enables Uniform Plating in Anode-Free Solid-State Batteries

Anode-free solid-state batteries (AFSSBs) are a promising route toward achieving high energy density. In these cells, the anode contains no pre-stored lithium (Li). Instead, all Li inventory originates from the cathode and is freshly deposited onto a bare current collector during charging. However, achieving uniform and defect-free Li plating on this bare current collector remains a major challenging, often resulting in low Li plating/stripping efficiency and rapid capacity decay. Here, for the first time, operando neutron imaging is employed to visualize Li plating/stripping behavior in an anode-free full cell with LiNi 0.82 Mn 0.07 Co 0.11 O 2 (NMC) as the cathode. Operando measurements reveal that complete stripping of Li leaves isolated Li residues on the current collector, which degrades interfacial contact between the current collector and solid-state electrolyte. To mitigate this interfacial issue and promote more uniform Li deposition, we implement a discharge cutoff voltage strategy that intentionally retains a thin residual Li layer after stripping. This thin Li layer, serving as an in situ–formed seed layer, not only enables more homogeneous subsequent Li plating but also improves interfacial contact. As a result, the anode-free cell with a controlled discharge voltage of 3.5 V exhibits excellent long-term cycling stability, maintaining a discharge capacity of 116 mAh g -1 with a retention rate of 83.4% and an average Coulombic efficiency of approximately 99.9% after 430 cycles at 0.25 C. In contrast, the cell with a conventional discharge cutoff voltage of 2.8 V exhibits rapid capacity decay, retaining only 59.7 mAh g -1 after 50 cycles with a capacity retention of 40.7%. This work offers a practical strategy to unlock the long-term viability of anode-free solid-state batteries.

25 ENERGY STORAGE↗

Pressure-Tolerant 3D Anodes Enable Short-Circuit Prevention and Low Heat Generation in Argyrodite Solid-State Batteries

Solid-state batteries (SSBs) offer a safer, higher-energy-density alternative to lithium-ion batteries, yet commercialization is hindered by incompatibility with lithium metal. Here, to overcome these challenges, we developed a cost-effective, commercially available prelithiated micro carbon fiber framework (Li-Cf) anode featuring a high-pressure-tolerance, for use with argyrodite solid-state electrolytes (SSEs). This 3D structure accommodates uniform lithium deposition, simplifies cell assembly under elevated pressure, inhibits dendrite growth toward SSEs, reduces heat generation, and enhances overall compatibility. Notably, our architecture enables the cell to tolerate pressures up to 400 MPa without short-circuiting during assembly. Meanwhile, the 3D framework serves as a preferential pathway for lithium deposition, thereby reducing lithium growth toward the SSEs and mitigating the risk of dendrite formation in SSEs. Operando calorimetry and distribution of relaxation times analysis reveal that lithium morphology degradation at the interface with the SSEs is a key failure mechanism in lithium metal argyrodite SSBs, leading to increased diffusion resistance and heat generation. In contrast, the Li-Cf anode mitigates these issues by reducing both heat flux and charge transfer resistance. Full cells with LiNi 0.8 Co 0.1 Mn 0.1 O 2 /Li 6 PS 5 Cl/Li-Cf retain ~79% capacity after 600 cycles, demonstrating significantly improved cycling stability and strong potential for practical energy storage applications.

25 ENERGY STORAGE↗