Search NASA⌕ Search

SEARCH · Search NASA

Results for “Suppressing metal corrosion”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Suppressing metal corrosion through identification of optimal crystallographic plane for Zn batteries

Direct use of metals as battery anodes could significantly boost the energy density, but suffers from limited cycling. To make the batteries more sustainable, one strategy is mitigating the propensity for metals to form random morphology during plating through orientation regulation, e.g., hexagonal Zn platelets locked horizontally by epitaxial electrodeposition or vertically aligned through Zn/electrolyte interface modulation. Current strategies center around obtaining (002) faceted deposition due to its minimum surface energy. Here, benefiting from the capability of preparing a library of faceted monocrystalline Zn anodes and controlling the orientation of Zn platelet deposits, we challenge this conventional belief. We show that while monocrystalline (002) faceted Zn electrode with horizontal epitaxy indeed promises the highest critical current density, the (100) faceted electrode with vertically aligned deposits is the most important one in suppressing Zn metal corrosion and promising the best reversibility. Such uniqueness results from the lowest electrochemical surface area of (100) faceted electrode, which intrinsically builds upon the surface atom diffusion barrier and the orientation of the pallets. These new findings based on monocrystalline anodes advance the fundamental understanding of electrodeposition process for sustainable metal batteries and provide a paradigm to explore the processing–structure–property relationships of metal electrodes.

25 ENERGY STORAGE↗
DOE OSTI2022

Suppressing Chemical Corrosions of Lithium Metal Anodes

In this study, the lithium metal anode is essential for next-generation high-energy-density rechargeable Li-metal batteries. Although extensive studies have been performed to prolong the cycle life of Li-metal batteries, the calendar life, which associates with the chemical corrosion of Li metal in liquid electrolytes, has not been quantitatively understood. Here, by combing the titration gas chromatography method and cryogenic focused ion beam, a quantitative relationship between the chemical corrosion rate and electrochemically deposited Li morphology in various liquid electrolyte systems is established. It has been identified that the corrosion rate is dominated by the porosity of the deposited Li. The larger the porosity of deposited Li has, the faster the corrosion rate will be. Strategies to mitigate the chemical corrosion on Li thus to extend the calendar life of Li-metal batteries are further proposed. By strictly controlling the stacking pressure during Li plating, Li deposits with ultra-low porosity can be achieved, suppressing the corrosion rate to 0.08 ± 0.16%/day compared with 1.71 ± 0.19%/day of the high-porosity Li.

25 ENERGY STORAGE↗
DOE OSTI2024

Fast Oxygen Redox Kinetics Induced by CoO 6 Octahedron With π –Interaction in P2–Type Sodium Oxides

Enhancing the kinetics of lattice oxygen redox (LOR) in P2-type layered sodium oxide cathodes is crucial for the advancement of sodium-ion batteries (SIBs) with superior energy and power densities. Electronic structure regulation stands out as a highly effective approach to address the inherent limitations of P2-type layered oxides with LOR, including sluggish kinetics, phase transitions, voltage hysteresis, and local structural distortion. In this work, a strategy involving the introduction of CoO 6 octahedra with π-interaction into Na 0.6 Li 0.1 Fe 0.3–x Co x Mn 0.6 O 2 (x = 0, 0.15, 0.3) cathodes to facilitate Na-ion transport is proposed. Furthermore, the impact of FeO 6 octahedra with σ-interaction in P2-type cathodes on electrochemical performance is comprehensively investigated. Through multimodal in-situ and ex-situ characterization techniques, it is revealed that Co–O with π-interaction effectively mitigates P2-OP4 phase transitions by strengthening Na–O, reduces voltage hysteresis, and stabilizes the local structure. Consequently, Na 0.6 Li 0.1 Co 0.3 Mn 0.6 O 2 demonstrates enhanced Na-ion diffusion kinetics, leading to improved rate performance and a reversible capacity of 55 mAh g –1 at 10 C, significantly outperforming cathodes with Fe–O σ-interaction. Moreover, when coupled with hard carbon, the full cell achieves a remarkable energy density of 395 Wh kg –1 (on cathode) at 0.1 C, with a capacity retention of 75% over 100 cycles at 1 C.

25 ENERGY STORAGE↗
DOE OSTI2025

X-ray Diffraction Studies of Single-Crystal Materials for Broad Battery Applications

Single-crystal materials have attracted growing interest in battery research due to their well-defined crystallographic orientation, absence of grain boundaries, and enhanced mechanical and electrochemical stability. This Review provides a comprehensive overview of recent advances in the synthesis, structural evolution, and performance optimization of single-crystal electrodes and solid electrolytes. Particular focus is placed on the application of advanced X-ray diffraction (XRD) techniques, including operando synchrotron diffraction, reciprocal space mapping, and Bragg coherent diffraction imaging, which have enabled in-depth investigations of lattice strain, cation disorder, phase transitions, and defect formation. Representative case studies across Ni-rich layered oxides, spinel-type cathodes, and garnet-based electrolytes are examined to highlight the structural features unique to single crystals. Additionally, the synergistic integration of XRD with machine learning, tomography, and spectroscopy is discussed as a powerful direction for real-time analysis and predictive modeling. Furthermore, these insights provide critical guidance for the rational design of high-performance single-crystal materials in lithium, sodium, and solid-state battery systems.

25 ENERGY STORAGE↗
DOE OSTI2025

Constraining Interlayer Slipping in P2-Type Layered Oxides with Oxygen Redox by Constructing Strong Covalent Bonds

Lattice oxygen redox (LOR) in P2-type layered oxides is an effective strategy to break through the limit of energy density of conventional cathodes due to its high redox potential (>4 V vs. Na + /Na) as well as extra capacity. Nevertheless, LOR induced local structure distortion and irreversible phase transitions cause serious electrochemical performance degradation, hindering the practical applications. In this work, we propose that the generation of the OP4 phase can be replaced with the Z phase by introducing Sb element with higher ionic potential and strong covalent bonds within the TMO 6 octahedron. Z phase transition is realized by constraining interlayer slipping between adjacent TM layers compared to OP4, which reduces the strain in the layered structure, lowers the Na+ diffusion energy barrier and creates more efficient Na+ diffusion channels. Consequently, Sb-substituted oxides demonstrates excellent kinetics, rate capability (79 mAh g -1 at 1 A g -1 ) in half cell and a high energy density of 487 Wh kg -1 (on cathode) in full cell.

25 ENERGY STORAGE↗
DOE OSTI2025

Mitigating X-ray-induced damage for accurate analysis of battery cathodes using transmission X-ray microscopy

Here, we investigate the impact of X-ray-induced damage on the evolution of battery cathodes using synchrotron transmission X-ray microscopy. In an operando coin cell, exposure to the X-ray beam can induce bubble formation, potentially rendering cathode particles electrochemically inactive and displacing particles from their initial position. However, utilizing external pressure on a pouch cell can mitigate bubble formation and its associated effects.

25 ENERGY STORAGE↗
DOE OSTI2022

Electrocatalytic water oxidation performance in an extended porous organic framework with a covalent alliance of distinct Ru sites

The rational synthesis of durable, earth-abundant efficient electrocatalysts for the oxygen evolution reaction (OER) from water is one of the most important routes for storing renewable energy and minimizing fossil fuel combustion. The prime hurdles for effectively utilizing commercial RuO 2 as (OER) electrocatalysts are its very low stability, catalyst deactivation, and high cost. In this work, we explored a Ru-integrated porous organic polymer (Ru@Bpy-POP) by a facile one-pot Friedel–Crafts alkylation strategy between redox-active (Ru(demob) 3 Cl 2 ) and a carbazole unit, which is composed of unique features including an extended framework unit, isolated active sites, and tunable electrode kinetics. Ru@Bpy-POP can serve as a bridge between a Metal–Organic Framework (MOF) and POP-based catalytic systems with a balanced combination of covalent bonds (structural stability) and open metal sites (single site catalysis). Ru@Bpy-POP, deposited on a three-dimensional nickel foam electrode support, exhibits a promising electrocatalytic OER activity with an ultra-low ruthenium loading compared to a benchmark RuO 2 catalyst, providing an overpotential of about 270 mV to reach 10 mA cm –2 in an alkaline medium. Moreover, a high current density of 248 mA cm –2 was achieved for the Ru@Bpy-POP catalyst at only 1.6 V (vs. RHE), which is much higher than 91 mA cm –2 for commercial RuO 2 . The robust, albeit highly conjugated, POP framework not only triggered facile electro-kinetics but also suppressed aggregation and metallic corrosion during electrolysis. In particular, the benefits of covalent integration of distinct Ru sites into the framework can modulate intermediate adsorption and charge density, which contributes to its exceptional OER activity. All of the critical steps involved in OER are complemented by Density Functional Theory (DFT) calculations, which suggest that electrocatalytic water oxidation proceeds from a closed-shell configuration to open-shell electronic configurations with high-spin states. Finally, these open-shell configurations are more stable than their closed-shell counterparts by 1 eV, improving the overall catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Average hydrodynamic radius analysis reveals critical solvation thresholds in high-concentration lithium electrolytes

Understanding the solvation structures of lithium salts in carbonate- and ether-based electrolytes is central to explaining the exceptional stability of high-concentration electrolytes (HCEs) and localized high-concentration electrolytes (LHCEs). Conventional techniques such as vibrational spectroscopy and one-dimensional NMR provide only limited information, typically restricted to coordination ratios and ion-pair distributions, without revealing the actual size and mass of solution complexes. Here, in this study, we introduce an average hydrodynamic radius (AHR) analysis based on internally referenced DOSY NMR, which enables direct estimation of the average volume and molecular weight of lithium–solvent complexes in solution. Using LiFSI–EMC and LiFSI–EMC–TTE electrolytes, we demonstrate that the onset of effective lithium metal stabilization and aluminum corrosion suppression coincides with the formation of very large complexes, whose average volume exceeds 300 times that of free EMC molecules. This finding supports a new “blocking mechanism,” wherein bulky solvated complexes impede direct solvent access to reactive surfaces. The AHR analysis thus not only clarifies the fundamental origin of HCE and LHCE effectiveness, but also provides a broadly applicable experimental framework for probing complex solvation structures and guiding rational electrolyte design.

Concentrated electrolytes↗
DOE OSTI2026

Ultra-Low Amounts of Transition Metals in Carbon-Based Catalysts Improve Their Alkaline OER Performance: A Systematic Study

The pursuit of green hydrogen production highlights a persistent gap in electrocatalyst research: while academic efforts prioritize cost-efficiency via activity enhancement, industrial viability demands greater emphasis on electrochemical stability. Carbon-based electrocatalysts, particularly those incorporating transition metals, have shown promise in alkaline oxygen evolution (OER) due to their high activity, cost-efficiency, and resource-efficiency. However, these catalysts suffer from insufficient stability under oxidizing conditions compared to pure transition metal catalysts due to erosion of the carbon support resulting from carbon corrosion, among other degradation mechanisms. In this systematic study, the influence of ultra-low amounts (<1 wt %) of iron, cobalt, nickel, and their most common combinations on the stability of a hydrothermally derived, N-doped carbon support and the overall catalyst performance during alkaline OER is systematically explored. By identifying critical stability descriptors and correlating them with synthesis conditions and catalyst properties, primary and secondary corrosion pathways are unraveled. Subsequently, through careful adjustment of carbonization temperature and composition of incorporated transition metals, overall catalyst corrosion can be suppressed immensely. Especially, the inclusion of Ni and Fe is paramount for the formation of stable catalyst materials under laboratory conditions (10 mA/cm 2 in 0.1 M KOH), which is surprisingly unconstrained by the degree of graphitization of the carbon support. Mixing this electrochemically stable material with a graphitic carbon powder results in an excellent stability of over 400 h at 100 mA/cm 2 in 1 M KOH, implying great potential for the future improvement of carbon-based electrodes under oxidizing conditions toward industrial application.

N-doped carbon↗
DOE OSTI2020

Improving Lithium Metal Composite Anodes with Seeding and Pillaring Effects of Silicon Nanoparticles

Metallic lithium (Li) anodes are crucial for the development of high specific energy batteries yet plagued by their poor cycling efficiency. Electrode architecture engineering is vital for maintaining a stable anode volume and suppress Li corrosion during cycling. In this paper, a reduced graphene oxide “host” framework for Li metal anodes is further optimized by embedding silicon (Si) nanoparticles between the graphene layers. They serve as Li nucleation seeds to promote Li deposition within the framework even without pre-stored Li. Meanwhile, the LixSi alloy particles serve as supporting “pillars” between the graphene layers, enabling a minimized thickness shrinkage after full stripping of metallic Li. Combined with a Li compatible electrolyte, 99.4% Coulombic efficiency over ~600 cycles is achieved, and stable cycling of a Li||NMC532 full cell for ~380 cycles with negligible capacity decay is realized.

Wang, Hansen↗
DOE OSTI2020

Near-Field Corrosion Interactions between Glass and Corrosion Resistant Alloys

This study explores the corrosion interactions between model nuclear waste glass materials and corrosion resistant alloys, under conditions that simulate the near field of a nuclear waste repository. The interactions between the corrosion of stainless steel (SS) 316, alloy G30, or alloy 625, and international simple glass or soda-lime silica glass are systematically studied. The dissimilar materials were exposed in close proximity to each other in different electrolytes at 90 oC. After exposure, the glass surface exposed near metals showed different regimes of corrosion, with distinct surface morphologies and chemistries that were likely affected by the local environment created by the localized corrosion of metals. Surface and solution analyses showed that the corrosion rate of glass was enhanced by the presence of metals. Infrared spectroscopy data suggested the local build-up of stresses in the contact area of glass, which may lead to the mechanical instability of the glass alteration layer. On the other hand, the effect of glass on metal corrosion is strongly dependent on the leaching solution. In electrolytes containing abundant aggressive anions such as Cl-, glass seems to suppress the localized corrosion of SS by the precipitation of a Si-rich surface film that protects the SS substrate from solutions. However, in less aggressive electrolytes, the corrosion rate of SS was increased by the presence of glass corrosion products. Overall, our study showed that the hidden and localized damage on glass in contact with metals may enhance the release of incorporated radionuclides compared to typical uniform glass corrosion. Therefore, more attention should be paid to the corrosion interactions between metals and glass under repository conditions.

Guo, Xiaolei↗
DOE OSTI2021

Complementary Electrolyte Design for Li Metal Batteries in Electric Vehicle Applications

In this report a complementary electrolyte system with 0.8 M lithium bis(fluorosulfonylimide) (LiFSI) salt and 2 wt % lithium perchlorate (LiCLO4) additive in fluoroethylene carbonate (FEC)/ethyl methyl carbonate (EMC) solution enables not only stable cycling of lithium metal batteries (LMBs) with practical loading (<30 μm lithium anode, cathode loading > 4 mAh/cm 2 ) but also outstanding degradation stability toward the end of cycle life when compared to the conventional electrolyte. Although the use of LiFSI salt can increase the electrolyte conductivity and lengthen the cycle life of LMBs, the aged lithium anode morphology formed by the sacrificial decomposition of LiFSI is highly porous, leading to an abrupt cell capacity drop toward the end of cycling. Moreover, the inability to stop aluminum corrosion by the LiFSI-based electrolyte also causes cracking of the cathode tab during prolonged cycling. It is observed that a highly porous aged lithium consumed electrolyte at a higher rate, leading to the dry-out of electrolyte solvents. On the contrary, dense aged lithium anode morphology increased the localized current applied on the lithium, causing the formation of lithium dendrite. Thus, porosity control is the key to enhance battery performance. In this complementary system, LiClO 4 was introduced as an advanced additive to not only improve the capacity retention rate but also mitigate the abrupt capacity drop toward the end of cycle life because LiClO 4 acted as a pore astringent reducing the porosity of the aged lithium metal anode to the desired level. Moreover, the addition of LiClO 4 can also suppress the AI corrosion, allowing stable high-voltage cycling of LMBs. The synergistic effect of combining LiFSI salt and a LiClO 4 additive leads to an electrolyte system that can facilitate the application of high-energy LMBs with practical electrode loading.

25 ENERGY STORAGE↗
DOE OSTI2024

Potential–Dependent BDAC Adsorption on Zinc Enabling Selective Suppression of Zinc Corrosion for Energy Storage Applications

Utility-scale zinc (Zn) batteries are a promising solution to address the problem of intermittency of renewable energy sources; however, Zn-metal anodes in these batteries suffer from capacity loss due to spontaneous corrosion of the Zn especially when high-surface area anode configurations are employed. Additionally, Zn dendrites are known to form during battery charging limiting the cycle-life of these batteries. Electrolyte additives have been explored that prevent aforementioned issues, but these too come at a cost, i.e., surface-blocking additives polarize the electrode surface leading to loss in the voltaic and energy efficiencies of the battery. In this contribution, a novel electrolyte additive, benzyldimethylhexadecylammonium chloride (BDAC), is investigated for its ability to suppresses corrosion of Zn in an acidic (pH = 3) electrolyte. An attribute of BDAC distinct from previously studied additives is that it selectively suppresses electrochemical activity when the Zn electrode is at its corrosion potential; however, during high-rate Zn deposition (charging) or stripping (discharging), BDAC is essentially deactivated and thus it does not appreciably polarize the electrode surface, thus minimizing voltaic efficiency losses. This selective corrosion suppression behavior is explored using slow-scan voltammetry, which reveals hysteresis implying a potential- or current-dependent BDAC adsorption mechanism in which BDAC reaches higher surface coverages when the partial currents at the Zn surface are low (e.g., at or near the corrosion potential), but BDAC coverage is reduced considerably when the Zn deposition or stripping rates are increased. Numerical simulations of the BDAC diffusion-adsorption process corroborate this mechanism. Ramifications of our approach to the selective suppression of Zn dendrites are discussed.

25 ENERGY STORAGE↗
DOE OSTI2025

Anions in Corrosion: Influence of Polymer Electrolytes on the Interfacial Ion Transfer Kinetics of Cu at Au(111) Surfaces

The corrosion kinetics of metals in the presence of polymer electrolytes—which are often used in devices for the electrochemical production of hydrogen, hydrocarbons, and alcohols—is convoluted by transport and ill-defined reactive interfaces which mask the fundamental reaction kinetics. Underpotential-deposited monolayers of Cu at Au(111) surfaces provide a structurally welldefined active site for interfacial ion transfer, with a fixed number of sites available for adsorption. Here, we investigate the adsorption behavior of Cu at Au(111) surfaces across a series of sulfate and sulfonate electrolytes, to understand how anion structure influences the kinetics of elementary interfacial ion-transfer reactions. The influence of anion structure is most significant at high adsorbate coverage, with similar adsorption isotherms and kinetics observed for all three molecular sulfates and sulfonates. In contrast, a suspended perfluorosulfonic acid ionomer reduced both the equilibrium coverage of Cu as well as the standard exchange rate at Au(111) at low coverages of Cu. These results suggest that electrocatalyst corrosion is inhibited for metal nanoparticles supported at polymer electrolytes due to changes in adsorbate coverage as well as suppressed kinetics for interfacial ion transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Investigation of oxygen evolution reaction with 316 and 304 stainless-steel mesh electrodes in natural seawater electrolysis

Here, two commercially available stainless steel mesh substrates (316 SS and 304 SS) were evaluated as electrodes for oxygen evolution reaction (OER) in natural seawater electrolysis. The results show the 304 SS is less stable against corrosion under neutral (pH of 8.5) and low alkaline (0.1 M NaOH, pH of 12.8) seawater electrolytes because of the direct metal dissolution and chlorine evolution reaction (CER), and the 316 SS is superior to 304 SS in terms of electrocatalytic activity and resistance to corrosion under the same media. The performance of 304 SS is comparable to 316 SS under the high alkaline (1 M NaOH, pH of 13.7) seawater electrolyte, where the CER and metal dissolution are suppressed by OER. The overpotential for 304 and 316 SS is around 430 mV at 10 mA cm -2 , and the Tafel slopes are below 50 mV dec -1 under the high alkaline (1 M NaOH) seawater electrolyte, showing promising performance. The poor resistance to corrosion of 304 SS is attributed to the low Mo content, and it is supposed that the stability of both 304 and 316 SS can be improved further with the addition of Mo content. This work expands on promising substrates for natural seawater electrolysis, with cost and performance advantages.

Stainless-steel mesh↗
DOE OSTI2020

Low-temperature and high-rate-charging lithium metal batteries enabled by an electrochemically active monolayer-regulated interface

Stable operation of rechargeable lithium (Li)-based batteries at low temperatures is vital for cold-climate applications but is plagued with dendritic Li plating and unstable solid-electrolyte interphase (SEI). Here we report high-performance Li-metal batteries under low-temperature and high-rate-charging conditions. This is realized by utilizing a self-assembled monolayer of electrochemically active molecules on current collectors that regulates the nanostructure and composition of SEI and deposition morphology of Li metal anodes. A multilayer SEI containing a LiF-rich inner phase and amorphous outer layer effectively seals the Li surface in contrast to the conventional impassive SEI at low temperatures. As a result, galvanic Li corrosion and self-discharge were suppressed; stable Li deposition was realized from -60º to 45ºC; and a Li|LiCoO 2 cell with a capacity of 2.0 mAh cm -2 displayed a 200-cycle life at -15ºC with a recharge time of 45 minutes.

25 ENERGY STORAGE↗
DOE OSTI2022

Three-dimensional Zn-based alloys for dendrite-free aqueous Zn battery in dual-cation electrolytes

Aqueous zinc-ion batteries, in terms of integration with high safety, environmental benignity, and low cost, have attracted much attention for powering electronic devices and storage systems. However, the interface instability issues at the Zn anode caused by detrimental side reactions such as dendrite growth, hydrogen evolution, and metal corrosion at the solid (anode)/liquid (electrolyte) interface impede their practical applications in the fields requiring long-term performance persistence. Despite the rapid progress in suppressing the side reactions at the materials interface, the mechanism of ion storage and dendrite formation in practical aqueous zinc-ion batteries with dual-cation aqueous electrolytes is still unclear. Herein, we design an interface material consisting of forest-like three-dimensional zinc-copper alloy with engineered surfaces to explore the Zn plating/stripping mode in dual-cation electrolytes. The three-dimensional nanostructured surface of zinc-copper alloy is demonstrated to be in favor of effectively regulating the reaction kinetics of Zn plating/stripping processes. The developed interface materials suppress the dendrite growth on the anode surface towards high-performance persistent aqueous zinc-ion batteries in the aqueous electrolytes containing single and dual cations. This work remarkably enhances the fundamental understanding of dual-cation intercalation chemistry in aqueous electrochemical systems and provides a guide for exploring high-performance aqueous zinc-ion batteries and beyond.

25 ENERGY STORAGE↗