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DOE OSTI2025

Mitigating Transition Metal Dissolution from Mn-rich Cathodes: Influence of Processing and Testing Methods

Manganese-rich oxides continue to gain interest with respect to the development of Earth-abundant options for lithium-ion cathodes. Of the unique challenges that hinder the respective performance of various classes of such materials, manganese dissolution still stands as a common theme. The work herein explores Li 3 PO 4 as a robust surface protection layer on a prototypical, Co-free, manganese-rich cathode in the way of a lithium- and manganese-rich oxide. The study highlights the critical importance of synthesis and processing in realizing optimal performance of a given surface treatment by comparing sol-gel and atomic layer deposition methods. Furthermore, cycling protocols are emphasized as a critical factor in adequately gauging the efficacy of surface protection strategies to mitigate manganese dissolution and the subsequent electrochemical consequence. Optimized Li 3 PO 4 coatings coatings on lithium- and manganese-rich cathode particles are shown to greatly mitigate capacity fade, impedance rise, pore/void formation and mechanical damage during long-term cycling.

Mallick, Subhadip [Argonne National Laboratory (AN↗

DOE OSTI2022

Methods for the production of cathode materials for lithium ion batteries

The present disclosure provides methods for producing cathode materials for lithium ion batteries. Cathode materials that contain manganese are emphasized. Representative materials include LixNi1-y-zMnyCozO2 (NMC) (where x is in the range from 0.80 to 1.3, y is in the range from 0.01 to 0.5, and z is in the range from 0.01 to 0.5), LixMn2O4 (LM), and LixMn2-yNiyO2 (LMN) (where x is in the range from 0.8 to 1.3 and y is in the range from 0.0 to 0.8). The process includes reactions of carboxylate precursors of nickel, manganese, and/or cobalt and lithiation with a lithium precursor. The carboxylate precursors are made from reactions of pure metals or metal compounds with carboxylic acids. The manganese precursor contains bivalent manganese and the process controls the oxidation state of manganese to avoid formation of higher oxidation states of manganese.

Huang, Baoquan↗

DOE OSTI2022

Methods for the production of cathode materials for lithium ion batteries

The present disclosure provides methods for producing cathode materials for lithium ion batteries. Cathode materials that contain manganese are emphasized. Representative materials include Li x Ni 1-y-z Mn y Co z O 2M (NMC) (where x is in the range from 0.80 to 1.3, y is in the range from 0.01 to 0.5, and z is in the range from 0.01 to 0.5), Li x Mn 2 O 4 (LM), and Li x Ni 1-y Mn y O 2 (LMN) (where x is in the range from 0.8 to 1.3 and y is in the range from 0.0 to 0.8). The process includes reactions of carboxylate precursors of nickel, manganese, and/or cobalt and lithiation with a lithium precursor. The carboxylate precursors are made from reactions of pure metals or metal compounds with carboxylic acids. The manganese precursor contains bivalent manganese and the process controls the oxidation state of manganese to avoid formation of higher oxidation states of manganese.

Huang, Baoquan↗

DOE OSTI2023

Methods for the production of cathode materials for lithium ion batteries

The present disclosure provides methods for producing cathode materials for lithium ion batteries. Cathode materials that contain manganese are emphasized. Representative materials include Li x Ni 1−y−z Mn y Co z O 2 (NMC) (where x is in the range from 0.80 to 1.3, y is in the range from 0.01 to 0.5, and z is in the range from 0.01 to 0.5), Li x Mn 2 O 4 (LM), and Li x Ni 1−y Mn y O 2 (LMN) (where x is in the range from 0.8 to 1.3 and y is in the range from 0.0 to 0.8). The process includes reactions of carboxylate precursors of nickel, manganese, and/or cobalt and lithiation with a lithium precursor. The carboxylate precursors are made from reactions of pure metals or metal compounds with carboxylic acids. The manganese precursor contains bivalent manganese and the process controls the oxidation state of manganese to avoid formation of higher oxidation states of manganese.

Huang, Baoquan↗

DOE OSTI2020

Solubility Testing to Support the Addition of Sodium Reactor Experiment Material to Sludge Batch 10

The Savannah River Site H-Canyon Facility is planning to discard dissolved Sodium Reactor Experiment (SRE) material into Tank 51 prior to Sludge Batch 10 (SB10). SB10 with the SRE material will be processed in the Defense Waste Processing Facility (DWPF) using the Nitric-Glycolic Acid (NGA) flowsheet. The DWPF Nuclear Criticality Safety Evaluation (NCSE) protects a 14:1 mass ratio of manganese to equivalent uranium-235 in both the solid and liquid phases during processing by requiring a 70:1 mass ratio in the feed. A concern was raised that freshly precipitated manganese in the SRE material will behave differently from the manganese in sludge during DWPF processing and potentially invalidate the criticality control. To mitigate risks to the DWPF criticality controls, the Savannah River National Laboratory (SRNL) performed a metals solubility test applicable to recently precipitated manganese and uranium, as would be expected with SRE transfers to SB10. The objective of this analysis is the tracking of partitioning of the primary fissile component (uranium-235) with the credited poison (manganese) between the aqueous and insoluble phases.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2020

Synergistic catalysis by Mn promoted ceria for molecular oxygen assisted epoxidation

Mesoporous manganese doped cerium oxide catalysts were prepared by an inverse micelle method with different manganese loadings. These materials exhibited superior activity for epoxidation of alkenes with molecular oxygen. Highest active 10MnCe material showed an activity of 80 % conversion and >99 % selectivity for cyclooctene epoxidation. The fluorite crystal structure which facilitates the high oxygen mobility, low temperature reducibility, homogeneous distribution of manganese on ceria, nanoparticle nature, higher number of oxygen vacancies, low valent states of manganese and cerium, and the ability to generate reactive oxygen species of the manganese doped cerium oxide could be correlated to the high catalytic activity. The reaction followed first order kinetics with a rate constant of 0.31 h –1 at 100 °C, and the activation energy turned out to be 10.5 kJ/mol. In conclusion, the mechanistic study revealed that the reaction proceeds via a unique mechanism which involves in situ generated superoxide and singlet oxygen species..

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Comparative analysis of the functional properties of human and mouse ferroportin

Ferroportin (Fpn)—expressed at the plasma membrane of macrophages, enterocytes, and hepatocytes—mediates the transfer of cellular iron into the blood plasma. Under the control of the iron-regulatory hormone hepcidin, Fpn serves a critical role in systemic iron homeostasis. Although we have previously characterized human Fpn, a great deal of research in iron homeostasis and disorders uses mouse models. By way of example, the flatiron mouse, a model of classical ferroportin disease, bears the mutation H32R in Fpn and is characterized by systemic iron deficiency and macrophage iron retention. The flatiron mouse also appears to exhibit a manganese phenotype, raising the possibility that mouse Fpn serves a role in manganese metabolism. At odds with this observation, we have found that human Fpn does not transport manganese, so we considered the possibility that a species difference could explain this discrepancy. We tested the hypothesis that mouse but not human Fpn can transport manganese and performed a comparative analysis of mouse and human Fpn. We examined the functional properties of human Fpn, mouse Fpn, and mutant mouse Fpn by using radiotracer assays in RNA-injected Xenopus oocytes. We found that neither mouse nor human Fpn transports manganese. Mouse and human Fpn share identical properties with respect to substrate profile, calcium dependence, optimal pH, and hepcidin sensitivity. We have also demonstrated that Fpn is not an ATPase pump. Our findings validate the use of mouse models of ferroportin function in iron homeostasis and disease.

Cell Biology↗

NASA NTRS1984

Study of high performance alloy electroforming

The first series of heat treated nickel manganese alloys are tested for mechanical properties at temperatures of 148.9 C (300 F) and 260 C (500 F). All material receives the same heat treatment in order to provide a common basis for comparison of results. Mechanical property performance improves with increasing manganese content in the alloy. Although all manganese bearing alloy is significantly superior to conventional electroformed nickel, samples containing over 3000 ppm manganese display outstanding ultimate and yield strengths while maintaining reasonably satisfactory ductility. Alloy containing over 6000 ppm of manganese is very competitive to Inconel 718 (mill annealed and age hardened) at all temperatures of interest, although ductility is not as great in the electrodeposited counterpart.

Malone, G. A.↗

NASA NTRS1984

Study of high performance alloy electroforming

Nickel-manganese alloy electrodeposits from an electrolyte containing more manganese ion than previously used is being evaluated at two bath operating temperatures with a great variety of pulse plating conditions. Saccharine was added as a stress reducing agent for the electroforming of several of the samples with highest manganese content. All specimens for mechanical property testing have been produced but are not through the various heat treatments as yet. One of the heat treatment will be at 343 C (650 F), the temperature at which the MCC outer electroformed nickel shell is stress relieved. A number of retainer specimens from prior work have been tested for hardness before and after heat treatment. There appears to be a fairly good correlation between hardness and mechanical properties. Comparison of representative mechanical properties with hardnesses are made for nickel-manganese electrodeposits and nickel-cobalt-manganese deposits.

Malone, G. A.↗

NASA NTRS1989

High performance alloy electroforming

Electroformed copper and nickel are used in structural applications for advanced propellant combustion chambers. An improved process has been developed by Bell Aerospace Textron, Inc. wherein electroformed nickel-manganese alloy has demonstrated superior mechanical and thermal stability when compared to previously reported deposits from known nickel plating processes. Solution chemistry and parametric operating procedures are now established and material property data is established for deposition of thick, large complex shapes such as the Space Shuttle Main Engine. The critical operating variables are those governing the ratio of codeposited nickel and manganese. The deposition uniformity which in turn affects the manganese concentration distribution is affected by solution resistance and geometric effects as well as solution agitation. The manganese concentration in the deposit must be between 2000 and 3000 ppm for optimum physical properties to be realized. The study also includes data regarding deposition procedures for achieving excellent bond strength at an interface with copper, nickel-manganese or INCONEL 718. Applications for this electroformed material include fabrication of complex or re-entry shapes which would be difficult or impossible to form from high strength alloys such as INCONEL 718.

Malone, G. A.↗

NASA NTRS2011

Effect of Reverse Bias Stress on Leakage Currents and Breakdown Voltages of Solid Tantalum Capacitors

The majority of solid tantalum capacitors are produced by high-temperature sintering of a fine tantalum powder around a tantalum wire followed by electrolytic anodization that forms a thin amorphous Ta2O5 dielectric layer and pyrolysis of manganese nitrite on the oxide to create a conductive manganese dioxide electrode. A contact to tantalum wire is used as anode terminal and to the manganese layer as a cathode terminal of the device. This process results in formation of an asymmetric Ta -- Ta2O5 -- MnO2 capacitor that has different characteristics at forward (positive bias applied to tantalum) and reverse (positive bias applied to manganese cathode) voltages. Reverse bias currents might be several orders of magnitude larger than forward leakage currents so I-V characteristics of tantalum capacitors resemble characteristics of semiconductor rectifiers. Asymmetric I-V characteristics of Ta -- anodic Ta2O5 systems have been observed at different top electrode materials including metals, electrolytes, conductive polymers, and manganese oxide thus indicating that this phenomenon is likely related to the specifics of the Ta -- Ta2O5 interface. There have been multiple attempts to explain rectifying characteristics of capacitors employing anodic tantalum pentoxide dielectrics. A brief review of works related to reverse bias (RB) behavior of tantalum capacitors shows that the mechanism of conduction in Ta -- Ta2O5 systems is still not clear and more testing and analysis is necessary to understand the processes involved. If tantalum capacitors behave just as rectifiers, then the assessment of the safe reverse bias operating conditions would be a relatively simple task. Unfortunately, these parts can degrade with time under reverse bias significantly, and this further complicates analysis of the I-V characteristics and establishing safe operating areas of the parts. On other hand, time dependence of reverse currents might provide additional information for investigation of the processes under reverse bias conditions. In practice, there were instances when, due to unforeseen events, the system operated at conditions when capacitors experience periodically a relatively small reverse bias for some time followed by normal, forward bias conditions. In such a case an assessment should be made on the degree to which these capacitors are degraded by application of low-voltage reverse bias, and whether this degradation can be reversed by normal operating conditions. In this study, reverse currents in different types of tantalum capacitors were monitored at different reverse voltages below 15%VR and temperatures in the range from room to 145 C for up to 150 hours to get better understanding of the degradation process and determine conditions favorable to the unstable mode of operation. The reversibility of RB degradation has been evaluated after operation of the capacitors at forward bias conditions. The effect of reverse bias stress (RBS) on reliability at normal operating conditions was evaluated using highly accelerated life testing at voltages of 1.5VR and 2 VR and by analysis of changes in distributions of breakdown voltages. Possible mechanisms of RB degradation are discussed.

Teverovsky, Alexander A.↗

DOE OSTI2022

Azospirillum brasilense Bacteria Promotes Mn2+ Uptake in Maize with Benefits to Leaf Photosynthesis

Azospirillum brasilense is a prolific grass-root colonizing bacteria well-known for its ability to promote plant growth in several cereal crops. Here we show that one of the mechanisms of action in boosting plant performance is through increased assimilation of the micronutrient manganese by the host. Using radioactive 52Mn2+ (t½ 5.59 d), we examined the uptake kinetics of this micronutrient in young maize plants, comparing the performance of three functional mutants of A. brasilense, including HM053, a high auxin-producing and high N2-fixing strain; ipdC, a strain with a reduced auxin biosynthesis capacity; and FP10, a strain deficient in N2-fixation that still produces auxin. HM053 had the greatest effect on host 52Mn2+ uptake, with a significant increase seen in shoot radioactivity relative to non-inoculated controls. LA-ICP-MS analysis of root sections revealed higher manganese distributions in the endodermis of HM053-inoculated plants and overall higher manganese concentrations in leaves. Finally, increased leaf manganese concentration stimulated photosynthesis as determined by measuring leaf fixation of radioactive 11CO2 with commensurate increases in chlorophyll concentration.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2022

Degradation Reduces Microbial Richness and Alters Microbial Functions in an Australian Peatland

Abstract Peatland ecosystems cover only 3% of the world’s land area; however, they store one-third of the global soil carbon (C). Microbial communities are the main drivers of C decomposition in peatlands, yet we have limited knowledge of their structure and function. While the microbial communities in the Northern Hemisphere peatlands are well documented, we have limited understanding of microbial community composition and function in the Southern Hemisphere peatlands, especially in Australia. We investigated the vertical stratification of prokaryote and fungal communities from Wellington Plains peatland in the Australian Alps. Within the peatland complex, bog peat was sampled from the intact peatland and dried peat from the degraded peatland along a vertical soil depth gradient (i.e., acrotelm, mesotelm, and catotelm). We analyzed the prokaryote and fungal community structure, predicted functional profiles of prokaryotes using PICRUSt, and assigned soil fungal guilds using FUNGuild. We found that the structure and function of prokaryotes were vertically stratified in the intact bog. Soil carbon, manganese, nitrogen, lead, and sodium content best explained the prokaryote composition. Prokaryote richness was significantly higher in the intact bog acrotelm compared to degraded bog acrotelm. Fungal composition remained similar across the soil depth gradient; however, there was a considerable increase in saprotroph abundance and decrease in endophyte abundance along the vertical soil depth gradient. The abundance of saprotrophs and plant pathogens was two-fold higher in the degraded bog acrotelm. Soil manganese and nitrogen content, electrical conductivity, and water table level (cm) best explained the fungal composition. Our results demonstrate that both fungal and prokaryote communities are shaped by soil abiotic factors and that peatland degradation reduces microbial richness and alters microbial functions. Thus, current and future changes to the environmental conditions in these peatlands may lead to altered microbial community structures and associated functions which may have implications for broader ecosystem function changes in peatlands.

Environmental Sciences & Ecology↗

DOE OSTI2020

Removal of Na + and Ca2 + with Prussian blue analogue electrodes for brackish water desalination

Desalination of brackish water sources is critical to addressing the growing global freshwater demand. One promising approach is electrically driven desalination using intercalation electrodes. While intercalation electrodes have been widely researched for energy storage applications, only a small subset of those materials is suitable for desalination. In this work, we report the synthesis, characterization, and in-device testing of three Prussian blue analogue intercalation compounds: copper, manganese, and zinc hexacyanoferrate with formulas K x M[Fe(CN) 6 ] z ·nH 2 O (M = Cu, Mn, Zn). The desalination performance for each of these materials against carbon electrodes is reported for Na + intercalation and for Ca 2+ intercalation using 1000 ppm NaCl and 1000 ppm CaCl 2 feed solutions, respectively. While the copper and manganese analogs showed promising performance for Na + and Ca 2+ intercalation, the zinc compound was unstable and underwent rapid dissolution. Manganese hexacyanoferrate showed the best desalination performance in terms of salt removal capacities and salt removal rates with NaCl while copper hexacyanoferrate performed the best with CaCl 2 . The manganese analog proved to be the most stable intercalation material, retaining 83% and 72% of its salt removal capacity after 280 cycles in NaCl and CaCl 2 feed solutions respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Fate of arsenic during the interactions between Mn-substituted goethite and dissolved Fe(II)

Geogenic arsenic has become a globally-distributed groundwater contaminant, liberated from the weathering of arsenic-bearing sulfide minerals and often transported to aquifer sediments adsorbed to iron oxides. Among the iron oxides, goethite (α-FeOOH) is uniquely important for the fate of arsenic because of its widespread abundance, stability, and high affinity for binding arsenic. Goethite is ubiquitous in soils and sediments and often contains substituted elements, including manganese. Structural manganese may affect the surface reactivity and redox capacity of goethite and alter the mechanisms of recrystallization catalyzed by dissolved Fe(II), potentially affecting arsenic adsorption. Here, this study examined the fate of As(V) during the interactions between dissolved Fe(II) and Mn-substituted goethites at pH 4 and 7 as well as associated changes in arsenic speciation. At pH 7, the addition of dissolved Fe(II) initially increases the adsorption of As(V) onto Mn-bearing and Mn-free goethites. For the Mn-substituted goethites, the adsorbed As(V) slowly releases to solution at longer aging times. Fe(II) addition at pH 4 slightly increases As(V) uptake by Mn-substituted goethites, with differences in total sorption correlating with the Mn content in goethite. The addition of Fe(II) releases substantial dissolved manganese but the amount solubilized is higher at pH 4 compared to 7, suggesting that the presence of adsorbed As(V) may substantially promote the Mn release at pH 4. X-ray absorption fine structure spectroscopy shows that arsenic is stabilized as As(V) in all the samples and adsorbed on goethite via a bidentate binuclear mechanism. Fitting results show that the binding distance and coordination numbers are stable in Mn-free goethite and Mn-substituted goethite samples; the effect of substituted Mn on the surface complex structure is minor. High resolution transmission electron microscopy and X-ray diffraction confirm that no secondary ferrous arsenate minerals precipitate under both pH conditions. This study improves our understanding of the Fe(II)-As(V) interactions on iron oxides, and demonstrates that the substituted cations such as manganese may quantitatively alter the geochemical fate of arsenic during the reaction of dissolved Fe(II) with Fe(III) oxides.

58 GEOSCIENCES↗

DOE OSTI2023

Redox Mechanisms and Migration Tendencies in Earth-Abundant 0.7Li 2 MnO 3 ·0.3LiFeO 2 Cathodes: Coupling Spin-Resolved X-ray Absorption Near Edge and X-ray Absorption Fine Structure Spectroscopies

We report the use of iron 1s3p resonant X-ray emission processes to conduct spin-selective, high-energy resolution fluorescence detected X-ray absorption near-edge spectroscopy (HERFD-XANES) on an iron-containing, lithium- and manganese-rich, fully earth-abundant cathode material, Li 1.3 Mn 0.5 Fe 0.2 O 2 (0.7Li 2 MnO 3 ·0.3LiFeO 2 ). Coupling this technique with conventional Mn K-edge XANES and detailed extended X-ray absorption fine structure (EXAFS) analysis from both the Mn and Fe vantage points, we gain fundamental insights into the redox processes and migration tendencies of transition metals in this cathode material at the bulk level. We show that during the first charge, Fe 3+ undergoes oxidation to form Fe 4+ prior to the activation plateau. Toward the end of activation, a significant fraction of the iron is present as tetrahedral Fe 3+ . This observation reveals that iron migration from octahedral to tetrahedral sites and iron reduction are initiated during activation. Upon first discharge from the activated state, a continuous and overlapping reduction of both Fe and Mn is observed, with Fe largely restored back as an octahedrally coordinated Fe 3+ . The manganese local environment gradually changes to a distorted cooperative Jahn–Teller Mn 3+ structure during discharge, with the clear presence of two Mn–O as well as two Mn–Mn correlation distances at 2.0 V. The significant reduction of manganese in the very first discharge is distinctly different from that seen in typical nickel-based lithium-manganese-rich materials but is similar to that observed for pure Li 2 MnO 3 . In conclusion, these findings shed light on key structure–property correlations in the cathode material and point to a causative relationship between the redox mechanisms as well as structural changes endured by the material and relatively poor performance during extended electrochemical cycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Earth-abundant Li-ion cathode materials with nanoengineered microstructures

Manganese-based materials have tremendous potential to become the next-generation lithium-ion cathode as they are Earth abundant, low cost and stable. Here we show how the mobility of manganese cations can be used to obtain a unique nanosized microstructure in large-particle-sized cathode materials with enhanced electrochemical properties. By combining atomic-resolution scanning transmission electron microscopy, four-dimensional scanning electron nanodiffraction and in situ X-ray diffraction, we show that when a partially delithiated, high-manganese-content, disordered rocksalt cathode is slightly heated, it forms a nanomosaic of partially ordered spinel domains of 3–7 nm in size, which impinge on each other at antiphase boundaries. The short coherence length of these domains removes the detrimental two-phase lithiation reaction present near 3 V in a regular spinel and turns it into a solid solution. This nanodomain structure enables good rate performance and delivers 200 mAh g –1 discharge capacity in a (partially) disordered material with an average primary particle size of ~5 µm. The work not only expands the synthesis strategies available for developing high-performance Earth-abundant manganese-based cathodes but also offers structural insights into the ability to nanoengineer spinel-like phases.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Unraveling the Structure and Composition of Li 4 Mn 2 O 4.5 (Li 2 O·Li 0.667 Mn 1.333 O 2 ) Electrodes for Lithium Batteries Using a High-Temperature Synthesis Approach

This paper addresses the debate about the composition and structure of a lithium-rich manganese oxide electrode with a fully disordered rock salt component, Li 4 Mn 2 O 5 (or Li 2 O·2LiMnO 2 ), first reported by Freire et al. in 2016; it is typically prepared by a high-energy ball milling procedure. It has now been demonstrated that, when prepared at 800°C, the formula of this compound is Li 4 Mn 2 O 4.5 , alternatively Li 2 O·Li 0.667 Mn 1.333 O 2 , or close thereto. The cubic, disordered Li 0.667 Mn 1.333 O 2 (or Li 0.333 Mn 0.667 O) rock salt component, in which the manganese ions adopt an average oxidation state of 2.5+, transforms to a clearly-defined spinel configuration during electrochemical cycling. The electrochemical activation process that occurs during the initial charge reaction includes the oxidation of the manganese ions by oxygen released by the Li 2 O component between 4.5 and 4.6 V. In complete contrast, nickel- and nickel-cobalt-substituted electrodes, such as Li 2 O·2LiMn 0.5 Ni 0.5 O 2 (Li 4 MnNiO 5 ) and Li 2 O·2LiMn 0.475 Ni 0.475 Co 0.050 O 2 (Li 4 Mn 0.95 Ni 0.95 Co 0.10 O 5 ), in which the manganese ions adopt a tetravalent state, have completely disordered rock salt components that are electrochemically inactive.

25 ENERGY STORAGE↗