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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Changing chemistry of particulate manganese in the near- and far-field hydrothermal plumes from 15°S East Pacific Rise and its influence on metal scavenging

Dissolved Mn(II) in the hydrothermal plume is known to be microbially oxidized to form Mn(III/IV) oxides, and the Mn oxides scavenge other trace elements in seawater. In the GEOTRACES GP16 cruise, dissolved Mn (dMn) and particulate Mn (pMn) were found to be transported over 4000 km westwards from the Southern Eastern Pacific Rise. Previous studies in this plume showed different removal rates of dMn and pMn as well as pMn size distribution between the near-field (<80 km from the ridge axis) and far-field (>80 km) plumes. In order to understand Mn cycling in these plumes, spatial distribution, oxidation states, and mineral structures of Mn in small size fraction (SSF; 0.8–51 μm) and large size fraction (LSF; >51 μm) particles from the near-field and far-field plumes were examined using micro X-ray fluorescence spectrometry (μ-XRF), X-ray absorption near-edge structure spectroscopy (XANES), chemical species mapping, and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the near-field plume, pMn in the SSF is dominated by oxidized Mn with Mn(III) fractions of ~30%. They are a mixture of δ-MnO 2 and triclinic birnessites that is known to be formed as a result of autocatalytic Mn(II) oxidation at the surface of freshly-formed δ-MnO2, suggesting that both microbial and autocatalytic Mn oxidation occur in the near-field plume. The LSF pMn in the near-field plume is also oxidized and often found in large aggregates several hundreds of μm in size. These aggregates settle out in the near-field and during transport, and are not found in the far-field plume. In the far-field plume where Mn oxides are not newly formed, pMn in the SSF is oxidized, but their Mn(III) fractions are smaller than in the near-field pMn. Unlike the SSF, the far-field plume LSF pMn is dominated by reduced Mn, implying very slow aggregation of pMn in the far-field plume. The different characteristics of pMn between the near-field and far-field plumes affect its scavenging of other trace elements. In the near-field plume, Co, Mo, 231 Pa are associated with pMn, but not in the far-field plume. 231 Pa is adsorbed to pFe rather than pMn in the far-field plume, and Pb is adsorbed to pFe in the entire plume. The result shows that freshly-formed Mn oxides in the near-field plume have higher scavenging capacity than the far-field plume pMn. Our findings suggest that the mineralogical age of Mn oxides may be an important parameter that controls the scavenging of many other trace elements and isotopes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Nanoscale hydration in layered manganese oxides

Birnessite is a layered MnO2 mineral with a nanoscale interlayer region that accommodates layers of intercalated water. Variable distributions of Mn sites with oxidation states of II, III and IV are responsible for the high catalytic reactivity of birnessite in nature and as a valuable candidate for energy storage solutions. We here report water loading capabilities and the vibrational spectral signatures of two forms of birnessite of strongly contrasting particle size. Using X-ray diffraction we find that potassium-birnessite accommodates no more than one monolayer (1W) of water in its interlayer region. Molecular simulations show that this is an energetically favorable hydration state where interlayer potassium-water and direct water-birnessite interactions are greater than at other hydration levels. Simulations also suggest a stable 2W state but that is not achieved experimentally by contact with water vapor. Finally, this work provides a means to predict the distribution of adsorbed and interlayer water molecules using a recently developed composite model.

Cheng, Wei↗
DOE OSTI2021

Impact of Stabilizing Cations on Lithium Intercalation in Tunneled Manganese Oxide Cathodes

Stabilizing cations such as K + , Ba 2+ , and Ag + are known to provide charge neutrality and enhance structural stability in low-cost tunneled manganese dioxide (MnO 2 ) cathodes for Li ion batteries. However, a fundamental understanding of the role of these cations in the electrochemical performance of tunneled MnO 2 cathodes remains unclear, especially at low stabilizing cation concentrations. Here, we employ density functional theory (DFT + U) calculations to reveal the impact of stabilizing potassium cation (K + ) concentration on the structural stability, electronic properties, and kinetics of lithium transport in 2 x 2 tunneled manganese oxide (α-K y Mn 8 O 16 , at y = 0, 1, and 2) battery cathodes during lithium intercalation. Specifically, we provide insights into the effect of K + ions on several critical factors governing the electrochemical storage performance of tunneled MnO2 cathodes, including (a) energetically favorable Li+ host sites, (ii) Li + and electron transport capabilities, (iii) optimal intercalation pathways, crystal distortion, microstructural stability, and tunneled-to-layer phase transformation as a function of lithium content, and (iv) cell output voltage profile. Interestingly, we find that low K + concentrations (y ≤ 1) yield partially cation-deficient tunnels in the MnO 2 cathode. Such unique tunnel structures in the cathode enable (a) low kinetic barriers for Li transport, (b) excellent thermodynamic stability of the tunneled structure even at a high Li + loading (up to ~ 0.625 Li/Mn), and (c) good electronic conductivity facilitated by Jahn-Teller distortions; all of which are critical for achieving high capacity batteries with enhanced rate capability. Additionally, these results provide perspectives to design low-cost transition metal oxide cathodes for high-performance Li-ion batteries with excellent cycle life.

25 ENERGY STORAGE↗
DOE OSTI2020

Electrodeposited Zinc-based Films as Anodes for Aqueous Zinc Batteries

Zinc-based batteries have attracted extensive attention in recent years, due to high safety, high capacities, environmental friendliness, and low cost compared to lithium ion batteries. However, the zinc anode suffers primarily from dendrite formation as a mode of failure in the mildly acidic system. Herein, we report on electrochemically deposited zinc (ED Zn) and copper-zinc (brass) alloy anodes, which are critically compared with a standard commercial zinc foil. The film electrodes are of commercially relevant thicknesses (21 and 25µM). The electrodeposited zinc-based anodes exhibit low electrode polarization (~0.025V) and stable cycling performance in 50 cycle consecutive experiments from 0.26-10 mA cm-2 compared to commercial Zn foil. Coulombic efficiencies at 1 mA cm-2 were over 98% for the electrodeposited zinc-based materials and were maintained for over 100 cycles. Furthermore, full cells with an electrodeposited Zn/brass anode, EMD MnO2 cathode, in 1M ZnSO4 + 0.1M MnSO4 delivered capacities of 96.3, and 163 mAh g-1, respectively, at a 100 mA g-1 compared to 92.1 mAh g-1 for commercial Zn. The zinc-based anodes also show better rate capability, delivering full cell capacities of 35.9 and 47.5 mAh g-1 at high current of up to 3 A g-1. Lastly, the electrodeposited zinc-based anodes show enhanced capacity for up to 100 cycles at 100 mA g-1, making them viable anodes for commercial use.

Fayette, Matthew R.↗
DOE OSTI2025

Spatial and chemical heterogeneity in aqueous Zn/MnO 2 batteries: role of Zn and Mn containing complexes

Aqueous Zn/MnO 2 batteries are a promising, safe alternative for grid-scale energy storage, owing to their environmentally safe and low-cost nature. The dissolution–deposition reaction mechanism in a mild aqueous pH regime has recently gained significance due to its relevance in battery design. Comprehending both the specific locations and the way reaction progresses is crucial for efficient batteries. This study demonstrates that Zinc Hydroxy Sulfate (ZHS) formed during discharge primarily near the dissolved MnO2 particles. Acting as a host for charge reactants in subsequent cycles, the charge product morphology was visualized using operando X-ray fluorescence microscopy. After ∼400 hours of cycling, capacity fade was linked to the formation of a Zn–Mn core–shell phase which is attributed to an irreversible core phase in the electrode, visualized through three-dimensional chemical mapping. Altogether, this research underscores the importance of understanding local morphological evolution in designing electrodes and chemistries for advanced grid-scale energy storage technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Demethylation or Sorption? The Fate of Methylmercury in the Presence of Manganese Dioxide

Manganese oxide (MnO 2 ) amendments to mercury (Hg)-contaminated sediment have been shown to decrease methylmercury (MeHg) concentrations in sediment porewater. In the absence of solid-phase MeHg measurements, it is unclear whether the decreased porewater concentrations are due to inhibition of methylation, adsorption of the MeHg to the MnO 2 , demethylation of MeHg catalyzed by the MnO 2 , or some combination of these mechanisms. We conducted controlled laboratory experiments to determine whether MeHg losses from solution in the presence of amorphous MnO 2 are due to sorption or demethylation. In this work, we quantified MeHg in the dissolved phase and solid phase and found that no demethylation occurred. We used batch and isotherm experiments to determine MeHg sorption efficiency to MnO 2 in a variety of solutions with varying ionic strength and dissolved organic matter (DOM) concentration. Isotherms over an initial concentration range of 5–500 ng/L of MeHg showed no saturation effects. Increasing ionic strength from 0.012 M to 0.1 M produced relatively minor decreases in MeHg sorption. Increasing DOM concentrations from 0.64 to 16.4 mg C/L yielded substantial decreases in MeHg sorption. Under the experimental conditions, MnO2 is a less efficient MeHg sorbent compared to other sorbent materials, such as Thiol-SAMMS®, activated carbon, and biochar.

42 ENGINEERING↗
DOE OSTI2020

Materials Data on Mn(CO3)2 by Materials Project

MnO2(CO2)2 is Cyanogen Chloride-like structured and crystallizes in the monoclinic C2/c space group. The structure is zero-dimensional and consists of eight carbon dioxide molecules and four manganese hydroxide (mn(oh)2) molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Microbial Reduction of Manganese Oxides From AMD Solids for the Biomining of Critical Minerals / Rare Earth Elements

Abandoned Coal-Mine Drainage (AMD) is a source of critical minerals (CMs) that can be biomined to increase domestic CM production for the growing tech industry while mitigating current AMD hazardous waste. Pennsylvania has ~11,000 abandoned mines, ~500 of which are currently being treated with passive remediation systems (PRS), designed to increase the pH and precipitate AMD waste onsite. Manganese (Mn) that precipitates from AMD waste can co-precipitate with CMs, and the Mn and CMs will accumulate on the PRS solids over the treatment period. This results in high Mn/CM solids that could produce a valuable leachate if resolubilized. Mn reduction and solubilization can occur through microbial driven geochemical changes such as the acidification of the environment, and it is expected that Mn resolubilization will lead to a co-resolubilization of the CMs. Investigation and stimulation of this microbial resolubilization could result in an affordable CM release process that does not require chemical additives into the environment. However the microbial mechanisms that contribute to Mn resolubilization are poorly understood. Here, we have isolated bacteria capable of resolubilizing Mn from AMD PRS. Five of the bacteria isolates have been identified as Bacillus spp. and two as Corynebacterium spp. that ferment glucose to reduce/solubilize Mn MnO2 by acidogenesis. The bacterial isolates are also capable of solubilizing Mn and CMs (Y, Zr, Sb, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) from AMD PRS precipitated solids through their production of organic acids. Determining the microbial metabolism and genes involved in the resolubilization of manganese is crucial to optimize the biomining of CMs from AMD solid precipitants. This work addresses the growing need to develop novel CM recovery methods from domestic sources.

critical minerals↗
DOE OSTI2026

High waste loading glass formulation development for High-Mn HLW

One of the primary objectives of the work described herein was to develop and identify HLW glass compositions and glass forming additive blends that achieve high waste loadings and processing rates for high manganese HLW streams while maintaining acceptable glass properties. Another objective was to determine the effect of the form of manganese (MnO, MnO2, MnCO3) on feed processing properties, glass production rates, and product quality while vitrifying a high manganese HLW stream. This was accomplished through a combination of crucible-scale tests, vertical gradient furnace tests, and confirmation tests on a DM100 melter system.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Stabilized birnessite cathode for high power and high energy density applications

A battery comprises a housing, an electrolyte disposed in the housing, an anode disposed in the housing, a stabilized cathode disposed in the housing and comprising a cathode material. The cathode material comprises a composition selected from birnessite or layered-polymorph of manganese dioxide (δ-MnO2), the composition being stabilized by bismuth and copper ions, a conductive carbon, and a binder. The anode can be at least 50% (m/m) lithium, magnesium, aluminum, or zinc.

Yadav, Gautam G.↗
DOE OSTI2023

Ultrahigh-Loading Manganese-Based Electrodes for Aqueous Batteries via Polymorph Tuning

Manganese-based aqueous batteries utilizing Mn 2+ /MnO 2 redox reactions are promising choices for grid-scale energy storage due to their high theoretical specific capacity, high power capability, low-cost, and intrinsic safety with water-based electrolytes. However, the application of such systems is hindered by the insulating nature of deposited MnO 2 , resulting in low normalized areal loading (0.005–0.05 mAh cm -2 ) during the charge/discharge cycle. Here, in this work, the electrochemical performance of various MnO 2 polymorphs in Mn 2+ /MnO 2 redox reactions is investigated, and ε-MnO 2 with low conductivity is determined to be the primary electrochemically deposited phase in normal acidic aqueous electrolyte. It is found that increasing the temperature can change the deposited phase from ε-MnO 2 with low conductivity to γ-MnO 2 with two order of magnitude increase in conductivity. It is demonstrated that the highly conductive γ-MnO 2 can be effectively exploited for ultrahigh areal loading electrode, and a normalized areal loading of 33 mAh cm -2 is achieved. At a mild temperature of 50 °C, cells are cycled with an ultrahigh areal loading of 20 mAh cm -2 (1–2 orders of magnitude higher than previous studies) for over 200 cycles with only 13% capacity loss.

25 ENERGY STORAGE↗
DOE OSTI2022

High-Energy and Stable Subfreezing Aqueous Zn–MnO 2 Batteries with Selective and Pseudocapacitive Zn-Ion Insertion in MnO 2

One major challenge of aqueous Zn–MnO 2 batteries for practical applications is their unacceptable performance below freezing temperatures. Here, in this study, the use of simple Zn(ClO 4 ) 2 aqueous electrolytes is described for all-weather Zn–MnO 2 batteries even down to -60 °C. The symmetric, bulky ClO 4 - anion effectively disrupts hydrogen bonds between water molecules and provides intrinsic ion diffusion even while frozen, and enables ≈260 mAh g -1 on MnO 2 cathodes at -30 °C . It is identified that subfreezing cycling shifts the reaction mechanism on the MnO 2 cathode from unstable H+ insertion to predominantly pseudocapacitive Zn 2+ insertion, which converts MnO 2 nanofibers into complicated zincated MnO x that are largely disordered and appeared as crumpled paper sheets. The Zn 2+ insertion at -30 °C is faster and much more stable than at 20 °C, and delivers ≈80% capacity retention for 1000 cycles without Mn 2+ additives. In addition, simple Zn(ClO 4 ) 2 electrolyte also enables a nearly fully reversible and dendrite-free Zn anode at -30 °C with ≈98% Coulombic efficiency. Zn–MnO 2 prototypes with an experimentally verified unit energy density of 148 Wh kg -1 at a negative-to-positive ratio of 1.5 and an electrolyte-to-capacity ratio of 2.0 are further demonstrated.

25 ENERGY STORAGE↗
DOE OSTI2021

Atomistic Insights of Irreversible Li + Intercalation in MnO 2 Electrode

Tunnel-structured MnO 2 represents open-framed electrode materials for reversible energy storage. Its wide application is limited by its poor cycling stability, whose structural origin is unclear. We tracked the structure evolution of β-MnO 2 upon Li + ion insertion/extraction by combining advanced in situ diagnostic tools at both electrode level (synchrotron X-ray scattering) and single-particle level (transmission electron microscopy). The instability is found to originate from a partially reversible phase transition between β-MnO 2 and orthorhombic LiMnO 2 upon lithiation, causing cycling capacity decay. Moreover, the MnO 2 /LiMnO 2 interface exhibits multiple arrow-headed disordered regions, which severely chop into the host and undermine its structural integrity. Our findings could account for the cycling instability of tunnel-structured materials, based on which future strategies should focus on tuning the charge transport kinetics toward performance enhancement.

25 ENERGY STORAGE↗
DOE OSTI2024

Rational optimization of substituted α–MnO 2 cathode for aqueous zinc–ion battery

Density functional theory (DFT) is utilized to explore the effects of increasing concentrations of vanadium (V) and chromium (Cr) substitution on the discharge of α-MnO 2 cathode in hydrated zinc-ion batteries (ZIBs). During H + -intercalation and Zn 2+ -intercalation, Cr-substitution proves to be more effective than V-substitution in promoting discharge behaviors. Transitioning from Mn 0.875 Cr 0.125 O 2 , Mn 0.75 Cr 0.25 O 2 to Mn 0.625 Cr 0.375 O 2 is found to consistently enhance the discharge voltage, along with improved tunnel structure retention and volume expansion suppression. In comparison, the promoting effect of increasing V-substitution is relatively small at initial discharge stages and leads to degradation at later stages, primarily due to an increased concentration of unstable Mn 2+ ion. The superior effect of Cr-substitution is attributed to the unique atomic and electronic structures of substituted Cr 4+ and reduced Cr 3+ ions during discharge. These ions serve as active electron acceptors to limit the formation of Mn 3+ and Mn 2+ ions, and as anchors to stabilize the α-MnO 2 framework and intercalated H + /Zn 2+ ions, respectively. Finally, our study highlights fine-tuning through substitution to enhance the performance of α-MnO 2 -based cathode materials in ZIBs.

25 ENERGY STORAGE↗
DOE OSTI2021

1-D NiO nanorods pillared 2-D MnO 2 nanosheets as lithium-free cathode materials for charged-state lithium batteries

Theoretically monolayer MnO 2 sheets have an impressive high capacity of 616 mAh/g, but practically monolayer MnO 2 sheets have poor performances due partially to monolayer restacking. In this paper, we report the preparation of three-dimensional porous NiO nanorod pillared δ-MnO 2 nanosheets as integrated nanoarchitectures as lithium-free cathode materials. The as-synthesized NiO pillared δ-MnO 2 nanosheets have resulted in a moderately high specific capacity of 185 mA h g –1 , with more than 63% capacity retention after 200 cycles. In comparison, 2D MnO 2 nanosheets without NiO pillared structures only achieved a low initial capacity of 137 mA h g –1 , with just 17% capacity retention after 200 cycles. The dramatically improved electrochemical performances could be attributed to high surface areas with excellent porosity which provides more electrochemically active sites and thermodynamically favorable insertion pathways for the lithium ions. Furthermore, our results reveal that insertion of pillars is a promising strategy to explore in order to mitigate the restacking issues and achieve electrochemical performances close to theoretical values for monolayer MnO 2 .

25 ENERGY STORAGE↗
DOE OSTI2024

A comprehensive study on two types of supercapacitor composite electrodes comprising MnO 2 and activated carbon nanofibers: Self-supporting membrane and ground powder

Manganese dioxide (MnO 2 )@carbon composites have been attractively considered as electrode materials for supercapacitors (SCs) due to synergistic effects. This work systematically investigated the structure of MnO 2 @carbon nanofiber (CNF) composite electrodes with the different forms of CNFs and the corresponding electrochemical performance of SCs. In brief, novel activated carbon nanofibers were first fabricated by electrospinning the hydroxyl-containing poly(amic acid) solution, and then the preferred CNF material was decorated by MnO 2 crystals in the form of self-supporting membrane and ground powders, respectively. Additionally, the synthesis parameters were investigated and optimized based on the electrochemical performance of SCs. The results reveal that the powdered composite electrode exhibits a higher specific surface area of 501 m 2 g –1 compared to the self-supporting membrane composite electrode under the same conditions, resulting in a promising specific capacity of 214.1 mAh g –1 (770.8 Fg –1 ) in 6M KOH solution at 0.5 A g –1 . In addition, the capacitance of the symmetrical SC device assembled by G-HMC-1:3–80 reaches 179.8 Fg –1 , coupled with an energy density of 24.86 Whkg –1 at 230 Wkg –1 power density. This work provides valuable hints for designing SC composite electrode materials with outstanding performance.

25 ENERGY STORAGE↗
DOE OSTI2022

Calorimetry can detect the early onset of hydrolysis in hybrid supercapacitors with aqueous electrolytes

This study investigates the effect of cation species on the onset of electrolyte hydrolysis in hybrid supercapacitors with aqueous electrolytes using isothermal operando calorimetry. The cells consisted of a positive α-MnO 2 cryptomelane electrode and a negative activated carbon (AC) electrode with either 0.5 M K 2 SO 4 or 0.5 M Cs 2 SO 4 aqueous electrolytes. They were characterized using cyclic voltammetry and galvanostatic cycling. In addition, the instantaneous heat generation rate at each electrode was measured using a custom isothermal operando calorimeter. Heat generation associated with resistive losses (Joule heating) and reversible ion adsorption/desorption was clearly identified. For larger potential windows, an endothermic dip, attributed to the onset of hydrolysis, was observed at the positive α-MnO 2 electrode where K + and Cs + ions engaged in fast surface redox reactions. Interestingly, this endothermic dip appeared at 1.8 V and 2.0 V for K 2 SO 4 and Cs 2 SO 4 aqueous electrolytes, respectively. The difference in the stable operating potential window was attributed to thinner solvation shell around Cs + cation than for K + thus reducing the amount of water present near the electrodes as ions partially shed their solvation shells during adsorption. The early onset of hydrolysis could be observed by isothermal operando calorimetry before it could be observed with conventional electrochemical methods.

42 ENGINEERING↗