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At least 1,243 records · Page 69
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Deciphering the Evolution of Current Distribution in Hybrid Silver Vanadium Oxide / Carbon Monofluoride Cathodes within Lithium Primary Batteries

For batteries to function effectively all active material must be accessible requiring both electron and ion transport to each particle. A common approach to generating the needed conductive network is the addition of carbon to create a composite electrode. An alternative approach is the electrochemically induced formation of conductive reaction products where the electrochemically generated materials are in intimate contact with the active material contributing to effective connection of each active particle. Furthermore, this study probes silver vanadium oxide (Ag 2 V 4 O 11 , SVO), carbon monofluoride (CF x ), and hybrid SVO/CF x electrodes in lithium batteries. Ex situ XRD identifies Ag 0 as a reduction product from SVO and LiF from CF x that can be followed as a function of depth-of-discharge (DOD). Spatially-resolved operando energy dispersive x-ray diffraction reveals that the presence of SVO alleviates reaction heterogeneity in the electrodes which are electron transfer limited in the absence of sufficient Ag 0 . Synchrotron X-ray tomography on discharged cathodes reveals the distribution of silver particles where the particles are more closely spaced near the current collector indicating multiple nucleation sites for their formation. Finally, operando isothermal microcalorimetry is used to determine the heat dissipation of the parent and hybrid battery types. Using material enthalpy potentials, we determine the current distribution between the two active materials for the discharging hybrid cathode adding further insight to the diffraction analysis. Taken together, these results provide a comprehensive understanding of hybrid SVO/CF x cathodes and give guidance on optimal compositions that balance power and energy density considerations.

36 MATERIALS SCIENCE↗
DOE OSTI2015

The Effect of Potassium Impurities Deliberately Introduced into Activated Carbon Cathodes on the Performance of Lithium-Oxygen Batteries

Rechargeable lithium-air (Li-O 2 ) batteries have drawn much interest owing to their high energy density. We report on the effect of deliberately introducing potassium impurities into the cathode material on the electrochemical performance of a Li-O 2 battery. Small amounts of potassium introduced into the activated carbon (AC) cathode material in the synthesis process are found to have a dramatic effect on the performance of the Li-O 2 cell. An increased amount of potassium significantly increases capacity, cycle life, and round-trip efficiency. This improved performance is probably due to a larger amount of LiO 2 in the discharge product, which is a mixture of LiO 2 and Li 2 O 2 , resulting from the increase in the amount of potassium present. No substantial correlation with porosity or surface area in an AC cathode is found. Lastly, experimental and computational studies indicate that potassium can act as an oxygen reduction catalyst, which can account for the dependence of performance on the amount of potassium.

25 ENERGY STORAGE↗
DOE OSTI2016

An Effectively Activated Hierarchical Nano-/Microspherical Li 1.2 Ni 0.2 Mn 0.6 O 2 Cathode for Long-Life and High-Rate Lithium-Ion Batteries

Rechargeable lithium-ion batteries with high energy and high power density are required in the application of electric vehicles and portable electronics. Herein, we introduce a type of spherical Li-rich cathode material, Li1.2Ni0.2Mn0.6O2, assembled from uniform nanocubes by a facile polyvinylpyrrolidone (PVP)-assisted hydrothermal method. The material with a hierarchical nano-/microstructure exhibits stable high-rate performance. Furthermore, the precipitant (i.e., urea) and the structure-directing agent (i.e., PVP) effectively activated the Li2MnO3 components in the microscale material to achieve a high specific capacity of 298.5 mAh g-1 in the first cycle. This Li-rich cathode material still delivered 243 mAh g-1 at 0.1 C after 200 cycles and the capacity retentions at 0.5, 1, 2, and 5mC were 94.4, 78.7, 76.3, and 67.8 % after 150 cycles, respectively. The results make this Li-rich nano-/microstructure a promising cathode material for long-life and high-performance lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Air‐Stable High‐Voltage Li‐Ion Organic Cathode Enabled by Localized High‐Concentration Electrolyte

While lithium‐ion batteries have revolutionized the field of energy storage, their reliance on critical minerals such as cobalt and nickel raises significant concerns over resource availability and supply chain uncertainty. In this study, we revisit dithiin‐fused dilithium naphthazarin (5,8‐dihydroxy‐1,4‐naphthoquinone) (DNP‐Li) as a high‐voltage Li‐ion organic cathode and evaluate its performance in conjunction with localized high‐concentration electrolyte (LHCE). DNP‐Li exhibits remarkable air and thermal stability, a high operating potential of 3.55 V vs. Li + /Li, and a specific capacity of 232 mAh g −1 , positioning it as one of the most promising candidates among Li‐ion organic cathodes. Furthermore, the electrochemical behavior of DNP‐Li is strongly influenced by the electrolyte composition, giving distinct two‐plateau or four‐plateau voltage profiles accompanied by reversible or irreversible phase transitions in carbonate‐based or LHCE electrolyte formulations, respectively. The reduced solubility of DNP‐Li‐based redox intermediates in LHCE enhances cycling stability, achieving a capacity retention of 85% after 50 cycles at 0.1C and 75% after 160 cycles at 0.5C, demonstrating a significant improvement compared to the carbonate‐based electrolyte. This work highlights the critical role of solute–electrolyte interactions in modulating the electrochemical performance of multielectron small‐molecule organic cathodes, offering new pathways for advancing sustainable and high‐efficiency energy storage technologies.

Lakraychi, Alae Eddine [Department of Electrical a↗
DOE OSTI2020

Direct Nano‐Synthesis Methods Notably Benefit Mg‐Battery Cathode Performance

Abstract Rechargeable magnesium batteries are promising candidates for next‐generation electrochemical energy storage, but their development is severely hindered by sluggish solid‐state diffusion and significant desolvation penalties of the divalent cation. Studies suggest that nano‐sized electrode materials alleviate these issues by shortening diffusion lengths and increasing electrode/electrolyte interaction. Here, the effect of particle size and synthetic methodology on the electrochemical performance of four sulfide cathode materials in Mg batteries is investigated: layered TiS 2 , CuS, spinel Ti 2 S 4 , and CuCo 2 S 4 . In these sulfide hosts, the direct preparation of nano‐dimensional crystallites is critical to activate or improve electrochemistry. Even promising cathode materials can appear electrochemically inert when micron‐sized particles are investigated (e.g., CuCo 2 S 4 ), and mechanical milling leads to surface degradation of active material which severely limits performance. However, nano‐sized CuCo 2 S 4 prepared directly reaches a capacity nearly double that of ball‐milled material and delivers 350 mAh g −1 at 60 °C. This work provides synthetic considerations which may be crucial in the discovery and design of novel Mg cathode materials, so that promising candidates are not overlooked. By extension, in oxide materials where Mg 2+ diffusion is expected to be much more sluggish, this factor is anticipated to be even more important when screening for new hosts.

Blanc, Lauren E.↗
DOE OSTI2024

Enhancing the Reaction Kinetics and Stability of Co‐Free Li‐Rich Cathode Materials via a Multifunctional Strategy

Co-free Li-rich layered oxides (CFLLOs) with anionic redox activity are among the most promising cathode materials for high-energy-density and low-cost lithium-ion batteries (LIBs). However, irreversible oxygen release often causes severe structural deterioration, electrolyte decomposition, and the formation of unstable cathode-electrolyte interface (CEI) film with high impedance. Additionally, the elimination of cobalt elements further deteriorates the reaction kinetics, leading to reduced capacity and poor rate performance. Here, in this study, a multifunctional strategy is proposed, incorporating Li 2 MnO 3 phase content regulation, micro-nano structure design, and heteroatom substitution. The increased content of Li 2 MnO 3 phase enhances the capacity through oxygen redox. The smaller nanoscale primary particles induce greater tensile strain and introduce more grain boundaries, thereby improving the reaction kinetics and reactivity, while the larger micron-sized secondary particles help to reduce interfacial side reactions. Furthermore, Na⁺ doping modulates the local coordination environment of oxygen, stabilizing both the anion framework and the crystal structure. As a result, the designed cathode exhibits enhanced rate performance, delivering a capacity of 158 mAh g⁻¹ at 5.0 C and improved cyclic stability, with a high capacity retention of 99% after 400 cycles at 1.0 C. This multifunctional strategy holds great promise for advancing the practical application of CFLLOs in next-generation LIBs.

Co-free Li-rich layered oxide↗
DOE OSTI2018

Simultaneous oxygen and boron trifluoride functionalization of hexagonal boron nitride: a designer cathode material for energy storage

Covalent functionalization is a way to tune the electrochemical properties of hexagonal boron nitride (h-BN) monolayers. The wide bandgap insulator h-BN may become metallic conductor upon functionalization with strong oxidants, such as (fluorosulfonyl)oxy radicals (·OSO 2 F), as known since 1978 ( Bartlett et al in J Chem Soc Chem Commun 5:200, 1978), with electrical conductivity of 1.5 S/cm (Shen et al in J Solid State Chem 147:74, 1999) that greatly surpasses commercial cathode material Li x CoO 2 while retaining excellent ionic conductivity. Functionalized boron nitrides (FBN-s) have great potential for cathode applications in energy storage devices, for example, in solid-state batteries. While (fluorosulfonyl)oxy functionalization is unlikely to result in rechargeable cathodes, similarly to graphene fluoride (CF x ), some other FBN-s discussed here may do. In the present work, fluorene, oxygen and combined oxygen and boron trifluoride functionalizations are studied, on the basis of band structure calculations. Due to the open surfaces of FBN-s, fast ionic diffusion with Li, Na and Mg ions is possible, enabling batteries with voltages of 2.1–5.6 V, theoretical energy densities of 800–1200 Wh/kg and fast charge and discharge.

Chemistry↗
DOE OSTI2018

Plasma Nitriding of AISI 304 Stainless Steel in Cathodic and Floating Electric Potential: Influence on Morphology, Chemical Characteristics and Tribological Behavior

In direct current plasma nitriding (DCPN), the treated components are subjected to a high cathodic potential, which brings several inherent shortcomings, e.g., damage by arcing and the edging effect. In active screen plasma nitriding (ASPN) processes, the cathodic potential is applied to a metal screen that surrounds the workload, and the component to be treated is placed in a floating potential. Such an electrical configuration allows plasma to be formed on the metal screen surface rather than on the component surface; thus, the shortcomings of the DCPN are eliminated. In this work, the nitrided experiments were performed using a plasma nitriding unit. Two groups of samples were placed on the table in the cathodic and the floating potential, corresponding to the DCPN and ASPN, respectively. The floating samples and table were surrounded by a steel screen. The DCPN and ASPN of the AISI 304 stainless steels are investigated as a function of the electric potential. The samples were characterized using scanning electron microscopy with energy-dispersive x-ray spectroscopy, x-ray diffraction, atomic force microscopy and transmission electron microscope. Dry sliding ball-on-disk wear tests were conducted on the untreated substrate, DCPN and ASPN samples. The results reveal that all nitrided samples successfully produced similar nitrogen-supersaturated S phase layers on their surfaces. This finding also shows the strong impact of the electric potential of the nitriding process on the morphology, chemical characteristics, hardness and tribological behavior of the DCPN and ASPN samples.

36 MATERIALS SCIENCE↗
DOE OSTI2018

An insoluble iron complex coated cathode enhances direct electron uptake by Rhodopseudomonas palustris TIE-1

Microbial electrosynthesis (MES) is a promising bioelectrochemical approach to produce biochemicals. A previous study showed that Rhodopseudomonas palustris TIE-1 can directly use poised electrodes as electron donors for photoautotrophic growth at cathodic potentials that avoid electrolytic H2 production (photoelectroautotrophy). To make TIE-1 an effective biocatalyst for MES, we need to improve its electron uptake ability and growth under photoelectroautotrophic conditions. Because TIE-1 interacts with various forms of iron while using it as a source of electrons for photoautotrophy (photoferroautotrophy), here we tested the ability of iron-based redox mediators to enhance direct electron uptake. Our data show that soluble iron cannot act as a redox mediator for electron uptake by TIE-1 from a cathode poised at +100 mV vs. Standard Hydrogen electrode. We then tested whether an immobilized iron-based redox mediator Prussian blue (PB) can enhance electron uptake by TIE-1. Chronoamperometry indicates that cathodic current uptake by TIE-1 increased from 1.47 ± 0.04 to 5.6 ± 0.09 μA/cm 2 (3.8 times). Overall, our data show that immobilized PB can enhance direct electron uptake by TIE-1.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

High-performance aqueous zinc-ion hybrid capacitors based on 3D printed metal-organic framework cathodes

The zinc-ion hybrid capacitor is a promising energy storage device, but current overall capacity is limited by the capacitance of the carbon cathode. We have produced a hierarchically porous, nitrogen-doped carbon cathode with good cycling and mechanical stability by 3D printing and pyrolysis of the zinc-based metal–organic framework ZIF-8. When incorporated into a zinc-ion hybrid capacitor, we achieved an areal capacitance of 16.9 F cm -2 and energy density of 7.23 mW h cm -2 , outperforming zinc-ion hybrid capacitors based on conventional cathodes.

25 ENERGY STORAGE↗
DOE OSTI2024

Microsphere LiMn 0.6 Fe 0.4 PO 4 /C cathode with unique rod-like secondary architecture for high energy lithium ion batteries

LiMn x Fe 1-x PO 4 /C is considered a promising next-generation cathode material with significant commercial potential, inheriting the safety of LiFePO 4 while offering higher energy densities. However, the extremely low conductivity and the Jahn-Teller effect induced by Mn 3+ limit its practical capacity and rate performance. Effective modifications can be achieved through particle nanonization and uniform carbon coating. Here, in this work, we synthesized microspherical LiMn 0.6 Fe 0.4 PO 4 /C cathode materials using a hydrothermal method combined with spray drying carbon coating. The cathode material exhibits a microsphere structure composed of aggregated nanorods with a uniform 3 nm carbon coating, showing good dispersibility, small specific surface area and high tap density. In-situ diffraction analysis showed that expanding the single-phase solid solution region during (de)lithiation can reduce the energy barrier for electron transport, improve the kinetics of the (dis)charge process, and enhance both cycling and rate performance. The initial capacity at 0.1C can reach 155 mAh/g, and the capacity remains at 133.5 mAh/g with a retention rate of 97.1 % after 300 cycles. The synergistic effect of particle nanonization and uniform carbon coating endows the LiMn x Fe 1-x PO 4 /C material with excellent electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2020

Electron and proton conductivity of Fe-N-C cathodes for PEM fuel cells: A model-based electrochemical impedance spectroscopy measurement

Impedance spectra of a PEM fuel cell with three Fe-N-C cathodes have been measured under the H 2 /N 2 testing regime. The spectra have been fitted using a recently developed physics-based impedance model, which takes into account finite proton ($σ_p$) and electron ($σ_e$) conductivity of the oxygen-free cathode catalyst layer. Fitting allowed to extract numerical data for $σ_p$, $σ_e$, the double layer capacitance, and the inductance of cables used for measuring impedance spectra. The values of σp and σe are close to what previously found for standard Pt/C electrodes, which is found for the first time using PGM-free catalysts. The method enables simultaneous measurement of reference proton and electron conductivity of PEMFC cathode.

25 ENERGY STORAGE↗
DOE OSTI2016

Mechanical and electrochemical response of a LiCoO 2 cathode using reconstructed microstructures

As LiCoO 2 cathodes are charged, delithiation of the LiCoO 2 active material leads to an increase in the lattice spacing, causing swelling of the particles. When these particles are packed into a bicontinuous, percolated network, as is the case in a battery electrode, this swelling leads to the generation of significant mechanical stress. In this study we performed coupled electrochemical-mechanical simulations of the charging of a LiCoO 2 cathode in order to elucidate the mechanisms of stress generation and the effect of charge rate and microstructure on these stresses. Energy dispersive spectroscopy combined with scanning electron microscopy imaging was used to create 3D reconstructions of a LiCoO 2 cathode, and the Conformal Decomposition Finite Element Method is used to automatically generate computational meshes on this reconstructed microstructure. Replacement of the ideal solution Fickian diffusion model, typically used in battery simulations, with a more general non-ideal solution model shows substantially smaller gradients of lithium within particles than is typically observed in the literature. Using this more general model, lithium gradients only appear at states of charge where the open-circuit voltage is relatively constant. While lithium gradients do affect the mechanical stress state in the particles, the maximum stresses are always found in the fully-charged state and are strongly affected by the local details of the microstructure and particle-to-particle contacts. These coupled electrochemical-mechanical simulations begin to yield insight into the partitioning of volume change between reducing pore space and macroscopically swelling the electrode. Lastly, preliminary studies that include the presence of the polymeric binder suggest that it can greatly impact stress generation and that it is an important area for future research.

25 ENERGY STORAGE↗
DOE OSTI2021

Effect of Pressure and Temperature on Carbon Dioxide Reduction at a Plasmonically Active Silver Cathode

Here, carbon dioxide reduction at a plasmonically active silver cathode was investigated by varying the pressure and temperature at multiple applied potentials under both dark and illuminated conditions to understand the mechanism of selectivity changes driven by plasmon-enhanced electrochemical conversion. Carbon dioxide partial pressures (P Co 2 ) from 0.2 to 1 atm were studied during linear sweep voltammetry and chronoamperometry at -0.7, -0.9, and -1.1 V RHE . At a given applied overpotential the total current density increased with increasing P Co 2 in both the dark and the light, but there were significant differences in the Tafel behavior between dark and illuminated conditions. The reduction of CO 2 to carbon monoxide (CO) was found to have first-order behavior with respect to P Co 2 at all applied potentials in both the dark and the light, likely indicating no change in the rate-determining step upon illumination. Activity for the hydrogen (H 2 ) evolution reaction decreased with increasing P Co 2 at slightly different rates in the dark and the light at each applied potential, making it unclear if light is influencing CO or H 2 intermediate adsorbate coverage. Both formate and methanol production showed no dependence on P Co 2 under any conditions, but the true reaction orders may be masked by the much higher activity for CO and H 2 at the silver cathode. The investigation of product distribution with temperature at 14, 22, and 32°C at -0.7, -0.9, and -1.1 V RHE in both the dark and the light demonstrated that the selectivity changes observed upon illumination are not caused by local heating of the cathode surface.

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

Evaluation of electrochemical performance and redox activity of Fe in Ti doped layered P2-Na0.67Mn0.5Fe0.5O2 cathode for sodium ion batteries

Here, we report a wet synthesis-based titanium doping strategy to improve the structural stability and electrochemical performances, such as cycling stability and rate capability, of P2-type Na 0.67 Fe 0.5 Mn 0.5 O 2 layered oxide cathodes. Through Ti 4+ doping aimed at replacing some of the Mn and Fe atoms in the crystal structure, effective mitigation of the Jahn Teller distortion caused by active Mn 3+ before charging and Fe 4+ after charging was achieved. X-ray diffraction (XRD), Raman spectroscopy, Electrochemical Impedance Spectroscopy (EIS) and Mössbauer spectroscopy were used to investigate the effects of the Ti 4+ dopant before and after cycling. It was observed that Ti 4+ doping increased the Na layer thickness, minimized the lattice volume strain, showed better structural stability, minimally decreased Fe migration to the Na layer, and lowered charge transfer resistance in these P2-type cathodes. Overall, our reported synthesis methodology and electrochemical characterizations highlight the feasibility of Ti doping in sodium layered oxide P2-type cathodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Investigating the durability of a direct methanol fuel cell equipped with commercial Platinum Group Metal-free cathodic electro-catalysts

For the first time a long-term (500 h) durability study in direct methanol fuel cells (DMFCs) is carried out on a Platinum Group Metal-free (PGM-free) cathodic electro-catalyst commercially available on market. The electro-catalyst is tested for 500 h at a fixed cell voltage (0.3 V), recording the polarization curves during the operation. A drastic decrease in performance is observed after the first 100 h (from 220 to 75 mA cm –2 ); afterwards, the decrease is flatter, passing from 75 to 25 mA cm –2 (at 500 h). The causes of this performance degradation are investigated by postmortem physicochemical analyzes, such as X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) with X-ray energy dispersive analysis (EDX). Finally, possible reasons of degradation are indicated to be PGM-free catalyst aggregation, carbon and nitrogen species decrease, Ruthenium dissolution and migration from the anode to the cathode, poisoning both membrane and cathode catalyst.

25 ENERGY STORAGE↗
DOE OSTI2020

Single crystal cathodes enabling high-performance all-solid-state lithium-ion batteries

All-solid-state lithium-ion batteries (ASSLIBs) are receiving significant attention owing to their improved safety and energy density over liquid counterparts. However, single-crystal cathodes have never been investigated in ASSLIBs. In this work, single-crystal Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 (SC-NMC532) is used as the cathode material for ASSLIBs, which exhibits 6~14 times higher Li + diffusion coefficient than polycrystalline Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 (PC-NMC532). As a result, SC-NMC532 exhibits an initial specific capacity of 156.4 mAh.g -1 while PC-NMC532 shows an initial capacity of only 127.5 mAh.g -1 . After 150 cycles, SC-NMC532 retains the capacity of 94.5 mAh.g -1 . More impressively, under a high current density of 1.3 mA.cm -2 , SC-NMC532 exhibits a capacity of 82 mAh.g -1 , much higher than that of PC-NMC532 (2.1 mAh.g -1 ). This work demonstrates that single-crystal NMC cathodes could enable both high power density and high energy density of ASSLIBs.

25 ENERGY STORAGE↗
DOE OSTI2021

Computation-guided discovery of coating materials to stabilize the interface between lithium garnet solid electrolyte and high-energy cathodes for all-solid-state lithium batteries

All-solid-state batteries with a lithium metal anode, enabled by lithium garnet solid electrolytes such as Li 7 La 3 Zr 2 O 12 (LLZO), are a promising next-generation energy-storage technology. The further development of all-solid-state battery requires the integration of high-energy cathodes such as LiNi 1-x-y Mn x Co y O 2 (NMC) with the garnet solid electrolyte with stable and low-resistance interfaces, which requires a coating layer to stabilize the interface during high-temperature sintering and electrochemical cycling. In order to guide the future development of interfacial coatings, we perform high-throughput thermodynamic analyses based on first-principles computation to investigate the stability of LLZO garnet and high-energy NMC cathodes with a wide range of materials chemistries. Here our study reveals the factors governing the materials stability with LLZO garnet and NMC cathodes, and identifies the mechanisms of good coating layers stable with LLZO and NMC. In addition to classifying known coating layers, our study provides detailed guiding charts and multiple new materials systems as promising coatings for stabilizing LLZO—NMC interfaces to enable high-energy-density garnet-based all-solid-state batteries. Our demonstrated computation scheme and high-throughput analyses are generally applicable to investigate and screen coating materials for stabilizing interfaces in energy-related applications.

25 ENERGY STORAGE↗