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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Mapping of Heterogeneous Catalyst Degradation in Polymer Electrolyte Fuel Cells

Pt catalysts in polymer electrolyte fuel cells degrade heterogeneously as the catalyst particles are exposed to local variations throughout the catalyst layer during operation. State-of-the-art analytical techniques for studying degradation of Pt catalysts do not possess fine spatial resolution to elucidate such non-uniform degradation behavior at a large electrode level. A new methodology is developed to spatially resolve and quantify the heterogeneous Pt catalyst degradation over a large area (several cm ) of aged MEAs based on synchrotron X-ray microdiffraction. PEFC single cells are aged using voltage cycling as an accelerated stress test and the degradation heterogeneity at a micrometer length scale is visualized by mapping Pt catalyst particle size after voltage cycling. It is demonstrated in detail that the Pt catalyst particle size growth is non-uniform and follows the flow field geometry. The Pt particle size growth is greater in the area under the flow field land, while it is minimal in the area under the flow field channel. Additional non-uniformity is observed with the Pt particle size increasing more rapidly at the air outlet area than the Pt particle size at the inlet area.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Multiscale electro-chemo-mechanical model of high-capacity amorphous silicon anode material in sodium-ion batteries

The growing interest in sodium-ion batteries (SIBs) is fueled by their abundant resources and environmentally friendly nature, with amorphous silicon (a-Si) emerging as a promising anode material for enhancing capacity. However, the key challenge lies in sustaining reversible capacity during cycling. Here, in this work, we developed a multiscale electrochemical model incorporating an a-Si anode to elucidate the performance parameters of SIBs. Additionally, we integrated an electro-chemo-mechanical model at the particle level to capture stress generation, an essential factor in the degradation of high-capacity electrodes. Unlike existing models, our approach accounts for large-deformation chemo-mechanics at the particle scale and includes simulations under varying charge rates to explore multiscale behavior. The results reveal that coupled sodiation significantly prolongs complete cycling times and influences discharge dynamics, indicating that neglecting this coupling leads to an underestimation of actual capacity. Furthermore, we observed pronounced polarization effects at higher charge rates, resulting in heterogeneous stress distributions across the anode. With the identification of critical failure parameters for both active particles and binder materials, offering novel insights for mitigating degradation in high-capacity electrode systems.

Amorphous silicon anode↗
DOE OSTI2023

Improving the Long-term Cycle Performance of xLi 2 MnO 3 ·(1-x)LiMeO 2 /Li 4 Ti 5 O 12 Cells via Prelithiation and Electrolyte Engineering

Toward the development of high energy density and long lifetime batteries for behind-the-meter storage (BTMS) applications, Li- and Mn-rich layered oxide cathode (xLi 2 MnO 3 ·(1-x)LiMeO 2 , Me = Ni, Mn, and etc., LMR-NM) and Li 4 Ti 5 O 12 (LTO) anode system was examined. To mitigate the major degradation mechanisms at each electrode (i.e., loss of Li inventory (LLI) at the anode and transition metal dissolution and oxygen release at the cathode), two approaches were taken—prelithiating the LTO electrode and varying the electrolyte solvent compositions. The effect of prelithiation and electrolyte engineering on the long-term cycle performance of LMR-NM/LTO cells were systematically evaluated via electrochemical analyses and post-mortem characterizations. By using a prelithiated LTO anode and supplying additional Li to the system, the capacity retention of LMR-NM/LTO system was improved. The degree of enhancement was dependent on the types of electrolytes used, as their decomposition products determined the level of LLI. With increased capacity retention, however, the cathode was utilized to a greater extent, resulting in more severe loss of the cathode active material. Thus, all degradation mechanisms should be considered comprehensively when designing high performance LMR-NM/LTO cells to account for their complex interplay.

25 ENERGY STORAGE↗
DOE OSTI2020

Sm 0.5 Sr 0.5 CoO 3-δ Surface Modification of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ -Ce 0.9 Gd0.1 2-δ Composite Oxygen Electrodes for Solid Oxide Electrochemical Cells

La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3- δ -Ce 0.9 Gd 0.1 O 2- δ (LSCF-GDC) composite oxygen electrodes have been widely used in intermediate temperature (<700 °C) solid oxide cells, with composite usually providing better electrochemical performance than single-phase LSCF. However, LSCF-based electrodes are often observed to degrade over time due to Sr segregation. Here we present an impedance spectroscopy study comparing the degradation behaviors of LSCF-GDC and Sm 0.5 Sr 0.5 CoO 3- δ (SSC) infiltrated LSCF-GDC electrodes. The LSCF-GDC polarization resistance increases by ~5 times over ~1000 h at 650 °C. In contrast, the SSC-infiltrated electrode shows similar initial polarization resistance but much more stable performance. The impedance modeling results show that the improved stability is associated with the low frequency oxygen dissociative adsorption/desorption process. The results suggest that this adsorption/desorption process slows due to increased Sr segregation on LSCF over time, and that SSC does not degrade significantly due to Sr surface segregation.

Electrochemistry↗
DOE OSTI2023

Electrochemical Characterization of Degradation Modes of High-Voltage Li x Ni 0.33 Mn 0.33 Co 0.33 O 2 Electrodes

While deeply charged high-voltage cathodes can improve battery energy density, understanding and preventing any accelerated cell degradation is crucial to practical success. Here, to analyze the degradation of LiNi x Mn y Co 1–x–y O 2 (NMC) type material charged to 4.3 and 4.5 V, a physics-based model is applied to cycling data to obtain parameter estimates indicative of degradation modes, which are validated by simple electrochemical measurements and further interpreted by materials characterization. Growth rates of interfacial impedance and active material loss are greater at 4.5 V, as might be expected. However, when charged to 4.5 V, degradation rates are initially lower at a cycling C-rate of 1.0 C than at 0.5 C. Once degradation mode changes are quantified, simulations evaluate the contribution of individual degradation mode to performance losses and provide estimates of the energy-power correlation (Ragone plots) of cells after cycling.

25 ENERGY STORAGE↗
DOE OSTI2021

Fundamental Investigations of Mechanical and Chemical Degradation Mechanisms in Lithium Ion Battery Materials (Final Technical Report)

The objective of our effort under the DOE EPSCoR Implementation grant is to establish a comprehensive and internationally recognized research program at Brown University and University of Rhode Island in understanding degradation mechanisms and to improve the cycle and calendar life of lithium ion battery (LIB) materials. A series of basic investigations are undertaken to characterize the mechanical and chemical degradation mechanisms, which can help enable new higher capacity and longer lasting electrode designs. Controlling mechanical and chemical degradation is the primary challenge in developing the next generation of higher energy density batteries. The development of failure resistant battery microstructures will require a fundamental understanding of the evolution of stress, deformation, damage, and electrochemistry in battery materials during cyclic charging and discharging. In addition, controlling the reactions at the electrode/electrolyte interface is critical for the formation of a stable SEI layer. We address these issues through a combination of controlled experiments on model battery materials and practical composite electrodes, together with multi-scale computations. Our effort is organized into three focus areas that encompass many critical challenges in Lithium Ion Battery Technologies: (i) Mechanical properties, fracture and damage in electrode materials; (ii) Chemistry and Mechanics of Solid Electrolyte Interphase (SEI); (iii) Mechanical and Chemical Integrity of Solid-Solid Interfaces in Practical Electrodes.

25 ENERGY STORAGE↗
DOE OSTI2020

Enabling Stable Cycling of 4.2 V High-Voltage All-Solid-State Batteries with PEO-Based Solid Electrolyte

Poly(ethylene oxide) (PEO)-based solid electrolytes are expected to be exploited in solid-state batteries with high safety. Its narrow electrochemical window, however, limits the potential for high voltage and high energy density applications. In this paper, the electrochemical oxidation behavior of PEO and the failure mechanisms of LiCoO 2 -PEO solid-state batteries are studied. It is found that although for pure PEO it starts to oxidize at a voltage of above 3.9 V versus Li/Li + , the decomposition products have appropriate Li + conductivity that unexpectedly form a relatively stable cathode electrolyte interphase (CEI) layer at the PEO and electrode interface. The performance degradation of the LiCoO 2 -PEO battery originates from the strong oxidizing ability of LiCoO 2 after delithiation at high voltages, which accelerates the decomposition of PEO and drives the self-oxygen-release of LiCoO 2 , leading to the unceasing growth of CEI and the destruction of the LiCoO 2 surface. When LiCoO 2 is well coated or a stable cathode LiMn 0.7 Fe 0.3 PO 4 is used, a substantially improved electrochemical performance can be achieved, with 88.6% capacity retention after 50 cycles for Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 coated LiCoO 2 and 90.3% capacity retention after 100 cycles for LiMn 0.7 Fe 0.3 PO 4 . The results suggest that, when paired with stable cathodes, the PEO-based solid polymer electrolytes could be compatible with high voltage operation.

25 ENERGY STORAGE↗
DOE OSTI2022

Low-Oxidized Siloxene Nanosheets with High Capacity, Capacity Retention, and Rate Capability in Lithium-Based Batteries

The mechanical degradation experienced by Si electrodes during Li (de)alloying reactions can potentially be mitigated by using Si-based materials with layered 2D geometries. Such materials are expected to exhibit favorable mechanical properties and be capable of buffering the volume change associated with (de)lithitation. In this work, 2D siloxene nanosheets are synthesized using a facile topotactic reaction followed by ultrasonication as an exfoliation step. Here, detailed structural and chemical characterization via electron microscopy, X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy is conducted, revealing a low-oxidized siloxene nanosheet material with only 15% surface Si-oxide. The obtained siloxene nanosheets are tested as Li-ion negative electrodes in lithium-based electrochemical cells. The cells exhibit high rate capability with a capacity of 935 mAh g –1 at 3200 mA g –1 and ≈99.5% coulombic efficiency. The inclusion of fluoroethylene carbonate (FEC) in the electrolyte improves capacity retention over 200 cycles from 13% to 77% at 1000 mA g –1 . This behavior is attributed to the FEC decomposition forming a solid electrolyte interphase (SEI) with higher ion conductivity and robust LiF/Li x PO y F z content, as characterized via XPS Raman spectroscopy.

25 ENERGY STORAGE↗
DOE OSTI2026

Chemo-Mechanics of α-V 2 O 5 During Lithiation and Implications for Rechargeable Battery Cathodes

Chemo-mechanical degradation of layered oxide electrodes is strongly influenced by crystallographic anisotropy, local stress evolution, and ion insertion, yet the intrinsic mechanical response of layered materials remains incompletely understood. Indeed, most prior studies have focused on polycrystalline materials but single crystals enable direct observation of coupling between anisotropic ion diffusion and mechanical response. This study aims to determine how crystallographic anisotropy and lithiation affect deformation, fracture, and mechanical properties in single-crystal V 2 O 5 , and compares this behavior with polycrystalline counterparts. Polycrystalline V 2 O 5 thin films and single-crystal α-V 2 O 5 were studied using nanoindentation, scanning electron microscopy, focused ion beam cross-sectioning, and Raman spectroscopy. Single crystals were tested in pristine and chemically lithiated states, including experiments in which crystals were first plastically deformed via nanoindentation and subsequently lithiated. Polycrystalline films exhibited significantly higher hardness and elastic modulus than single crystals. Single crystals indented normal to the exposed (001) basal plane exhibited pronounced anisotropic deformation, including directional slip, crystallographically-guided cracking, anisotropic crack propagation, interlayer separation, and shear localization. Lithiation caused substantial softening, reduced hardness and modulus, and suppressed displacement bursts during nanoindentation, while previously indented regions showed crack formation and growth upon lithiation. Mechanical behavior of α-V 2 O 5 is strongly governed by crystallographic anisotropy and further altered by lithiation, with pre-existing deformation serving as a strong driver of fracture during ion insertion. These findings illuminate the coupling among ion insertion, deformation, and fracture in layered oxides and provide a basis for understanding and mitigating mechanical failure in electrochemical energy-storage materials.

Anisotropy↗
DOE OSTI2023

Consequences of utilizing a redox-active polymeric binder in Li-ion batteries

Development of new polymeric binders can help enable the use of silicon-rich anodes in Li-ion batteries, by providing stronger adhesion to the active material particles. The compositional features that improve interfacial interactions and mechanical properties can often impart electronic conductivity and redox activity to these polymers, which are generally seen as beneficial to cell performance. Alternatively, it is also possible that the addition of charge-transferring centers to the electrode can accelerate cell degradation. Here, we use an aromatic polyimide (∼320 mA h/g of reversible capacity) to explore how a redox-active conductive polymer can affect cell performance. We demonstrate that the lithiated polymer is less stable than the traditional binders upon storage, leading to increased rates of calendar aging. Furthermore, we determine that the adhesion properties of the polymer deteriorate upon repeated cycling, to an extent that is proportional to the degree of delithiation of the binder. More critically, we establish that progressive degradation of the redox behavior of the polymer leads to the release of “extra” Li + into the cell, which can give the false perception of good performance even under conditions of poor stability. In conclusion, our work suggests that redox-active conductive binders can sometimes be detrimental to cell performance, and that works evaluating new polymers must include careful experimental validation under realistic conditions.

25 ENERGY STORAGE↗
DOE OSTI2025

Durability Optimization of CO 2 Electrolyzers for Syngas Evolution

Recently, there has been an increased interest in mitigating anthropogenic CO 2 emissions through the electrochemical conversion of CO 2 into fuels and fuel feedstocks, including hydrogen gas (H 2 ), carbon monoxide (CO), and mixtures of the two to yield syngas. Commercial applications of these systems require high catalytic selectivity for the desired products, while exhibiting operational lifetimes exceeding thousands of hours. Advancements in this field have produced systems that display high selectivity of the desired products at faradaic efficiencies exceeding 95%. Despite the advancements made in CO 2 electrolysis, system durability remains a standing challenge in the field. CO 2 electrolyzer lifetimes are often limited by carbonate fouling, catalyst degradation, detrimental flooding of electrode microporous layers and anion exchange membrane (AEM) failures. In this report, a 5 cm 2 membrane electrode assembly (MEA) device is used to investigate potential failure modes and to optimize AEM CO 2 electrolyzer operation. Key findings of this study include the importance of CO 2 flow rate, use of a thin PiperION PTFE-reinforced membrane, optimizing compression to enhance contact under 40 in-lb compression, and the effect of more compressible, commercial iridium oxide anodes on system durability.

Abouremeleh, Mohammed H. [Lawrence Berkeley Nation↗
DOE OSTI2022

Effect of electrochemical cycling on microstructures of nanocomposite silicon electrodes using hyperpolarized 129 Xe and 7 Li NMR spectroscopy

The microstructural stability of composite electrodes during electrochemical cycling is critically important as it dictates the performance of Li-ion batteries. The issue becomes even more important for the high capacity alloying anode such as silicon that typically exhibits dramatic lithiation–delithiation-induced volume changes. The solid electrolyte interphase (SEI) layer formed on the active electrode surface has a profound effect on the overall microstructural stability of composite electrodes. An ideal SEI layer allows Li+ ions in and out of the electrode, but is an insulator to electrons, preventing the electrolyte from being further reduced. However, the SEI layers formed during initial lithiation may experience changes or degradation with subsequent cycling, adversely affecting the electrode performance. A combination of hyperpolarized 129 Xe and 7 Li nuclear magnetic resonance spectroscopies was applied to probe the microstructures of nanocomposite silicon electrodes at various stages of the lithiation–delithiation cycle. The results obtained from this study shed light on the degradation mechanism of nanocomposite Si electrodes upon electrochemical cycling and should prove useful in the effort to design more robust electrodes in the future.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Performance and Durability of Heavy-Duty Fuel Cell Systems with an Advanced Ordered Intermetallic ORR Alloy Catalyst and Novel Support

Ordered PtCo intermetallic (OIM) catalyst (L1 0 -PtCo/C) is a promising candidate as the oxygen reduction reaction (ORR) catalyst in hybrid fuel cell systems (FCS) for class-8 heavy duty (HD) trucks. Compared to a baseline annealed Pt on high surface area carbon (a-Pt/HSC) catalyst, its mass activity (MA) is 71% higher initially and 144% higher after 90,000 potential cycles in an accelerated stress test (AST). Analysis of the AST data indicates that the ORR kinetic constants do not change with aging and the degradation in the OIM catalyst activity is linearly proportional to the loss in the electrochemically active surface area (ECSA). Several operational strategies are investigated to mitigate catalyst degradation and achieve 25,000-h electrode lifetime and 2.5 kW g −1 Pt utilization on a HD truck duty cycle including load sharing with the hybrid battery, regulating the radiator fan power to maintain the coolant temperature close to 60 °C, clipping the maximum cell voltage below 850 mV, limiting the ECSA loss to 55%, and oversizing the active area of the membrane electrode assemblies by 20%. Drive cycle simulations indicate that the lifetime average voltage degradation rate is about 1.8 μV h −1 and the integrated stack and FCS drive cycle efficiencies decrease by 3.5 to 3.9%.

25 ENERGY STORAGE↗
DOE OSTI2020

Amorphous Pd-Loaded Ti 4 O 7 Electrode for Direct Anodic Destruction of Perfluorooctanoic Acid

In this work we present a novel Ti 4 O 7 -based electrode loaded with amorphous Pd clusters that achieve efficient anodic destruction of perfluorooctanoic acid (PFOA), a persistent water pollutant with significant environmental and human health concerns. These amorphous Pd clusters were characterized by the disordered, noncrystalline arrangement of Pd single atoms in close proximity, in contrast to crystalline Pd nanoparticles that have been often employed to tailor the electronic properties of an electrode. We found that the Ti 4 O 7 electrode loaded with amorphous Pd clusters significantly outperformed the Ti 4 O 7 electrode loaded with crystalline Pd particles due to enhanced electron transfer through dominant Pd–O bonds. Combined with the efficient binding of PFOA and its degradation intermediates to the fluorinated electrode surface, this electrode was capable of mineralizing PFOA and releasing fluoride as F – . The reaction pathway was found to proceed without involving reactive oxygen species and therefore was not quenched by common anions in complex natural water systems such as chloride ions.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Defluorination Mechanisms and Real-Time Dynamics of Per- and Polyfluoroalkyl Substances on Electrified Surfaces

Per- and polyfluoroalkyl substances (PFAS) are persistent environmental contaminants found in groundwater sources and a wide variety of consumer products. In recent years, electrochemical approaches for the degradation of these harmful contaminants have garnered a significant amount of attention due to their efficiency and chemical-free modular nature. However, these electrochemical processes occur in open, highly non-equilibrium systems, and a detailed understanding of PFAS degradation mechanisms in these promising technologies is still in its infancy. To shed mechanistic insight into these complex processes, we present the first constant-electrode potential (CEP) quantum calculations of PFAS degradation on electrified surfaces. These advanced CEP calculations provide new mechanistic details about the intricate electronic processes that occur during PFAS degradation in the presence of an electrochemical bias, which cannot be gleaned from conventional density functional theory calculations. We complement our CEP calculations with large-scale ab initio molecular dynamics simulations in the presence of an electrochemical bias to provide time scales for PFAS degradation on electrified surfaces. Taken together, our CEP-based quantum calculations provide critical reaction mechanisms for PFAS degradation in open electrochemical systems, which can be used to prescreen candidate material surfaces and optimal electrochemical conditions for remediating PFAS and other environmental contaminants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

A Low-Cost Iron-Based Current Collector for Alkaline Battery Electrodes

The use of three-dimensional porous nickel foam as the current collector of the nickel hydroxide electrode adds significantly to the cost of the nickel-based alkaline rechargeable batteries. Although iron is considerably less expensive than nickel, iron corrodes at the operating potential of the nickel hydroxide electrode. We have found that a 70–100 nm thick thermal coating of cobalt ferrite spinel protects the iron from corrosion. Such a coated iron substrate was found to be stable against corrosion even when polarized anodically at 10 mA cm -2 in 30% potassium hydroxide electrolyte for 1000 h. While the thermal coating of cobalt ferrite protected iron against corrosion, incorporation of lithium ions into the coating was found to enhance the electrical conductivity of the coating. XPS and EXAFS studies confirmed that the enhanced conductivity resulted from an increase in the population of Co 3+ in the ferrite spinel lattice. An inexpensive iron (steel) substrate protected by such a coating when used as a nickel hydroxide battery electrode exhibited a specific capacity of 0.25 Ah g -1 at C/5 discharge rate, comparable to a nickel hydroxide electrode based on a relatively expensive nickel foam substrate. The steel-based electrode also exhibited no noticeable degradation over 150 cycles at C/2 rate. This demonstration of a robust and economical steel substrate presents a unique opportunity for reducing the cost of the nickel hydroxide battery electrode in alkaline batteries

25 ENERGY STORAGE↗