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

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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Flexible and conductive waste tire-derived carbon/polymer composite paper as pseudocapacitive electrode

A method of making a supercapacitor from waste tires, includes the steps of providing rubber pieces and contacting the rubber pieces with a sulfonation bath to produce sulfonated rubber; pyrolyzing the sulfonated rubber to produce a tire-derived carbon composite comprising carbon black embedded in rubber-derived carbon matrix comprising graphitized interface portions; activating the tire-derived carbon composite by contacting the tire-derived carbon composite with a specific surface area-increasing composition to increase the specific surface area of the carbon composite to provide an activated tire-derived carbon composite; and, mixing the activated tire-derived carbon composite with a monomer and polymerizing the monomer to produce a redox-active polymer coated, activated tire-derived carbon composite. The redox-active polymer coated, activated tire-derived carbon composite can be formed into a film. An electrode and a supercapacitor are also disclosed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

MXene-Conducting Polymer Asymmetric Pseudocapacitors

Conducting polymers (CPs) are attractive pseudocapacitive materials which show the highest capacitance under positive potentials in aqueous protic electrolytes. One way to expand their voltage window (thus energy density) in aqueous electrolytes is to manufacture asymmetric supercapacitors using distinctly different anodes. However, CPs lack matching pseudocapacitive anode materials that can perform well in protic electrolytes (e.g., sulfuric acid). 2D titanium carbide (Ti 3 C 2 T x ), MXene, as a universal pseudocapacitive anode material for a range of CPs, such as polyaniline, polypyrrole, and poly(3,4-ethylenedioxythiophene) deposited on reduced graphene oxide (rGO) sheets, is reported here. All-pseudocapacitive organic–inorganic asymmetric devices with MXene cathodes and rGO–polymer anodes can operate in voltage windows up to 1.45 V in 3 m H 2 SO 4 . Most importantly, these devices show outstanding cycling performance, outperforming many reported asymmetric pseudocapacitors.

catalysis (heterogeneous)↗
DOE OSTI2020

Differentiating Double-Layer, Psuedocapacitance, and Battery-like Mechanisms by Analyzing Impedance Measurements in Three Dimensions

Electrochemical energy storage arises from processes that are broadly categorized as capacitive, pseudocapacitive, or battery-like. Advanced charge-storing materials that are designed to deliver high capacity at a high rate often exhibit a multiplicity of such mechanisms, which complicates the understanding of their charge-storage behavior. In this paper, we apply a “3D Bode analysis” technique to identify key descriptors for fast Li-ion storage processes, where AC impedance data, such as the real capacitance ($C'$) or phase angle ($Φ$), are represented versus the frequency ($f$) and a third independent variable, the applied DC cell voltage. For double-layer processes, a near-constant $C'$ or $Φ$ is supported across the entire voltage range, and the decrease in these values shows a near-linear decrease at higher $f$. For pseudocapacitance, an increase in $C'$ is delivered, accompanied by high $C'$ retention at higher $f$ compared to double-layer processes. Interestingly, the lower $Φ$ values, where $C'$ is highest, suggest that this is a key descriptor for pseudocapacitance, where high-rate charge storage is still facilitated within a kinetically limited regime. For battery-like processes, a high $C'$ is only observed at the voltage at which the material stores charge, while outside that voltage, $C'$ is negligible. The three-dimensional (3D) Bode analysis allows charge-storage dynamics to be mapped out in great detail with more delineation between mechanisms compared to the more frequently deployed kinetic analyses derived from cyclic voltammetry.

25 ENERGY STORAGE↗
DOE OSTI2017

The Role of Ru Redox in pH-Dependent Oxygen Evolution on Rutile Ruthenium Dioxide Surfaces

Rutile RuO 2 is known to exhibit high catalytic activity for the oxygen evolution reaction (OER) and large pseudocapacitance associated with redox of surface Ru, however the mechanistic link between these properties and the role of pH is yet to be understood. Here we report that the OER activities of the (101), (001) and (111) RuO 2 surfaces were found to increase while the potential of a pseudocapacitive feature just prior to OER shifted to lower potentials (“super-Nernstian” shift) with increasing pH on the reversible hydrogen electrode (RHE) scale. This behavior is in contrast to the (100) and (110) surfaces that have pH-independent Ru redox and OER activity. The link in catalytic and pseudocapacitive behavior illustrates the importance of this redox feature in generating active sites, building new mechanistic understanding of the OER.

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

A Parallel Kinetic Model for Surface and Bulk Charge Storage in ε -MnO 2 Pseudocapacitors

Pseudocapacitive materials such as manganese dioxide (MnO 2 ) are attractive for energy storage applications due to their ability to combine the fast kinetics of capacitors with the higher energy density of battery-type systems. However, the electrochemical behavior of MnO 2 remains difficult to interpret mechanistically, in part because existing models often fail to distinguish between surface-based redox processes and bulk intercalation mechanisms. In this work, we develop a physics-based model that represents MnO 2 pseudocapacitance as a linear combination of two independent, parallel electrochemical processes: (i) the surface or near-surface redox storage and (ii) lithium ion intercalation into the bulk material. These two processes are treated with distinct kinetic and thermodynamic parameters and are assumed to proceed independently. The total measured current is assumed to be the sum of these two partial currents. We validate the model using rate-dependent cyclic voltammetry experiments, demonstrating that it captures key trends and provides physically interpretable parameters reflecting the relative contributions of surface and bulk processes. By enabling a clear separation between these mechanisms, the model offers a useful framework for analyzing pseudocapacitive materials and can guide the rational design of high-performance energy storage electrodes.

Energy - Storage↗
NASA NTRS2012

Electrochemical Ultracapacitors Using Graphitic Nanostacks

Electrochemical ultracapacitors (ECs) have been developed using graphitic nanostacks as the electrode material. The advantages of this technology will be the reduction of device size due to superior power densities and relative powers compared to traditional activated carbon electrodes. External testing showed that these materials display reduced discharge response times compared to state-of-the-art materials. Such applications are advantageous for pulsed power applications such as burst communications (satellites, cell phones), electromechanical actuators, and battery load leveling in electric vehicles. These carbon nanostructures are highly conductive and offer an ordered mesopore network. These attributes will provide more complete electrolyte wetting, and faster release of stored charge compared to activated carbon. Electrochemical capacitor (EC) electrode materials were developed using commercially available nanomaterials and modifying them to exploit their energy storage properties. These materials would be an improvement over current ECs that employ activated carbon as the electrode material. Commercially available graphite nanofibers (GNFs) are used as precursor materials for the synthesis of graphitic nanostacks (GNSs). These materials offer much greater surface area than graphite flakes. Additionally, these materials offer a superior electrical conductivity and a greater average pore size compared to activated carbon electrodes. The state of the art in EC development uses activated carbon (AC) as the electrode material. AC has a high surface area, but its small average pore size inhibits electrolyte ingress/egress. Additionally, AC has a higher resistivity, which generates parasitic heating in high-power applications. This work focuses on fabricating EC from carbon that has a very different structure by increasing the surface area of the GNF by intercalation or exfoliation of the graphitic basal planes. Additionally, various functionalities to the GNS surface will be added that can exhibit pseudocapacitance. This pseudocapacitance exhibits faradaic (charge transfer) properties that can further increase the overall relative and volumetric capacitance of the material. A process is also proposed to use GNF as a precursor material to fabricate GNS that will be used as EC electrodes. This results in much better electrical conductivity than activated carbon. This is advantageous for high-pulsed-power applications to reduce parasitic heating. Larger average pore size allows more complete electrolyte wetting (faster charge transfer kinetics). These properties contribute to a lowered equivalent series resistance (ESR), increased specific power, shorter charging times, and decreased parasitic heating. The high density of basal plane edges provides nucleation sites for activation (addition of hydrophilic functional groups) that facilitate electrolyte wetting, and will contribute to pseudocapacitance.

Marotta, Christopher↗
DOE OSTI2023

Enhancing Charge Storage of Mo 2 Ti 2 C 3 MXene by Partial Oxidation

Abstract Driving the pseudocapacitive redox intercalation in 2DMXenes with neutral electrolytes is important for safer, more sustainable, and improved electrochemical charge storage. Single transition metal MXenes, such as Ti 3 C 2 , have shown great promise for energy storage, owing to their high conductivity and redox activity. Mixed metallic MXenes, such as out‐of‐plane ordered Mo 2 Ti 2 C 3 , have remained underexplored in energy storage because of the absence of redox activity in most of the electrolytes. Simultaneous structural modifications and instigating intercalation pseudocapacitance in neutral electrolytes could be a viable strategy for enhancing their electrochemical properties. Herein, a facile synthesis of partially oxidized Mo 2 Ti 2 C 3 MXene (PO‐Mo 2 Ti 2 C 3 ) exhibiting improved charge storage capability is demonstrated. Optical, structural, and spectroscopic analyses indicate the formation of oxide nanostructures upon thermal oxidation of Mo 2 Ti 2 C 3 . This leads to an enhanced energy storage capability with remarkably improved cyclability as well as a high Coulombic efficiency in a neutral LiCl electrolyte. This work highlights the importance of structural modifications of MXenes to enhance their charge storage and shows the promise of less explored double transition metal MXenes in energy storage.

Chemistry↗
DOE OSTI2017

Titanium Disulfide Coated Carbon Nanotube Hybrid Electrodes Enable High Energy Density Symmetric Pseudocapacitors

While electrochemical supercapacitors often show high power density and long operation lifetimes, they are plagued by limited energy density. Pseudocapacitive materials, in contrast, operate by fast surface redox reactions and are shown to enhance energy storage of supercapacitors. Furthermore, several reported systems exhibit high capacitance but restricted electrochemical voltage windows, usually no more than 1 V in aqueous electrolytes. Here, it is demonstrated that vertically aligned carbon nanotubes (VACNTs) with uniformly coated, pseudocapacitive titanium disulfide (TiS 2 ) composite electrodes can extend the stable working range to over 3 V to achieve a high capacitance of 195 F g -1 in an Li-rich electrolyte. A symmetric cell demonstrates an energy density of 60.9 Wh kg -1 —the highest among symmetric pseudocapacitors using metal oxides, conducting polymers, 2D transition metal carbides (MXene), and other transition metal dichalcogenides. Nanostructures prepared by an atomic layer deposition/sulfurization process facilitate ion transportation and surface reactions to result in a high power density of 1250 W kg -1 with stable operation over 10 000 cycles. In conclusion, a flexible solid-state supercapacitor prepared by transferring the TiS 2 –VACNT composite film onto Kapton tape is demonstrated to power a 2.2 V light emitting diode (LED) for 1 min.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Fabrication of CeO2/PANI composites for high energy density supercapacitors

Highlights: • Fabrication of CeO{sub 2}/PANI composite was successfully prepared using easy solution mixing method. • Combinational approaches of rare earth oxides with conducting polymer composites posses’ excellent pseudocapacitive nature. • Superior specific capacitance, rate capacitance and cyclic stability. • Outstanding performance of asymmetric and symmetric devices. - Abstract: Combinational approaches of rare earth oxides with conducting polymer composites have gained vast attention in supercapacitor field due to the outstanding pseudocapacitive property. Here we detail the redox reaction based on CeO{sub 2}/polyaniline nanostructure to grasp the superior electrochemical nature of the composite. The CeO{sub 2}/polymer nanostructure showed the improved specific capacitance of 1452 F g{sup −1} at 2 A g{sup −1} when compared to pristine CeO{sub 2} (927 F g{sup −1} at 2 A g{sup −1}). The composite also maintains excellent rate capacitance (875 F g{sup −1} at 10 A g{sup −1}) and good cyclic stability upto 1500 cycles at high current density of 20 A g{sup −1}. Symmetric and asymmetric supercapacitor devices were fabricated using CeO{sub 2}/ PANI as an electrode. Moreover, the asymmetric supercapacitor possesses excellent specific capacity (256 F g{sup −1} at 2 mV s{sup −1}) with high energy density (75 Whkg{sup −1}) and high power density (566 Wkg{sup −1}). These results suggest a potential usefulness of CeO{sub 2}/ PANI composite exploit as an efficient electrode for supercapacitor applications.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Electrochemical Hydrogen Evolution at Ordered Mo 7 Ni 7

Ni–Mo alloys containing up to ~15 mol % Mo are excellent non-noble electrocatalysts for the hydrogen evolution reaction (HER) in alkaline aqueous electrolytes. To date, studies have not addressed the details of HER activity of ordered Ni–Mo intermetallic compounds, which can contain a significantly larger fraction of Mo (up to 50 mol %) than can be accessed through high-temperature alloying. Here, we present a straightforward and facile synthesis of three phase-pure electrocatalyst powders using a precipitation–reduction approach: ordered Mo7Ni7, disordered Ni0.92Mo0.08, and pure Ni. The Ni0.92Mo0.08 alloy exhibited a nearly 10-fold higher mass-specific HER activity than either pure Ni or Mo7Ni7, where much of the difference could be attributed to relative surface area. Therefore, we attempted to quantify and account for differences in surface areas using electron microscopy, impedance spectroscopy, and gas adsorption measurements. These data suggest that Ni–Mo alloys and intermetallic compounds exhibit substantial pseudocapacitance at potentials near the onset of hydrogen evolution, which can cause impedance spectroscopy to overestimate the interfacial capacitance, and thus the electrochemically active surface area, of these materials. From these observations, we postulate Mo redox activity as the chemical basis for the observed pseudocapacitance of Ni–Mo composites. Furthermore, using gas adsorption measurements, rather than capacitance, to estimate active surface area, we find that ordered Mo7Ni7 is more intrinsically active than the Ni0.92Mo0.08 alloy, implying that Mo7Ni7 intermetallics with high surface area will also give higher mass-specific activities than alloys with comparable roughness.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Influences from solvents on charge storage in titanium carbide MXenes

We report that pseudocapacitive energy storage in supercapacitor electrodes differs significantly from the electrical double-layer mechanism of porous carbon materials, which requires a change from conventional thinking when choosing appropriate electrolytes. Here we show how simply changing the solvent of an electrolyte system can drastically influence the pseudocapacitive charge storage of the two-dimensional titanium carbide, Ti 3 C 2 (a representative member of the MXene family). Measurements of the charge stored by Ti 3 C 2 in lithium-containing electrolytes with nitrile-, carbonate- and sulfoxide-based solvents show that the use of a carbonate solvent doubles the charge stored by Ti 3 C 2 when compared with the other solvent systems. We find that the chemical nature of the electrolyte solvent has a profound effect on the arrangement of molecules/ions in Ti 3 C 2 , which correlates directly to the total charge being stored. Finally, having nearly completely desolvated lithium ions in Ti 3 C 2 for the carbonate-based electrolyte leads to high volumetric capacitance at high charge–discharge rates, demonstrating the importance of considering all aspects of an electrochemical system during development.

25 ENERGY STORAGE↗
DOE OSTI2021

Defect–Concentration–Mediated T–Nb 2 O 5 Anodes for Durable and Fast–Charging Li–Ion Batteries

Metastable orthorhombic niobium pentoxide (T-Nb 2 O 5 ) is a promising anode to fulfill the requirements for high-rate Li-ion batteries (LIBs). Stoichiometric T-Nb 2 O 5 is plagued by low electric conductivity and particle pulverization after repeated charge/discharge processes. In this work, oxygen vacancies are implanted into T-Nb 2 O 5 particles via acid immersion of Nb 2 O 5 ·nH 2 O with the formation of Lewis acid sites. The multiple characterizations and simulations reveal the lengthening of Nb–O bonds, and the transformation from NbO 7 pentagonal bipyramids and NbO 6 tetragonal bipyramids in T-Nb 2 O 5–x . The enrichment of oxygen vacancies endows T-Nb 2 O 5–x with higher electric conductivity, better electrochemical kinetics, larger pseudocapacitive contribution. O-doped graphitic C 3 N 4 is creatively proposed as a trace oxygen pump to repair excessive oxygen vacancies, and it also serves as a sacrifice template for Nb 2 O 5–x growth to construct a porous and monolithic electrode network. Defect-modulated Nb 2 O 5–x displays extraordinary cycling stability (164 mAh g –1 at 5 C after 1100 cycles), high capacity retention (104 mAh g –1 ) at an ultrahigh rate (25 C), and large areal capacity (0.74 mAh cm –2 ) under high mass loading (4 mg cm –2 ). The practical prospect is proved by Nb 2 O 5–x /LiNi 0.8 Co 0.1 Mn 0.1 O 2 full cells with high average platform (2.12 V) and high specific capacity (229 mAh g –1 ). Finally, the oxygen-defect modulation strategy on oxide anodes provides an alternative solution to fast-charging and durable LIBs.

25 ENERGY STORAGE↗
DOE OSTI2017

Engineering Ultrathin Polyaniline in Micro/Mesoporous Carbon Supercapacitor Electrodes Using Oxidative Chemical Vapor Deposition

In this work, oxidative chemical vapor deposition (oCVD) is demonstrated to enable the integration of nanometer-thin polyaniline (PANI) that significantly improves charge storage capacity of supercapacitors utilizing carbide-derived carbon (CDC) with a bimodal (micro/mesoporous) pore size distribution. To our knowledge, this work is the first reported synthesis of PANI via oCVD. The oCVD process allows for the integration of PANI into pores as small as 1.7 nm, and resulting CDC/PANI electrodes have a gravimetric capacitance more than twice that of bare CDC (136 F g -1 for 11 wt% of PANI in the CDC electrode versus 60 F g -1 for bare Mo 2 C-CDC at 10 mV s -1 ). This yields a PANI-only gravimetric capacitance of ≈690 F g -1 , which is close to the theoretical value of 750 F g -1 . The coating preserves the native electrode surface area and pore size distribution, while improving capacitance due to the faradaic redox reactions of PANI. Even at high scan rates of over 100 mV s -1 , the added pseudocapacitance from PANI remains evident. Finally, the composite electrode exhibits good cyclability, decreasing to 90% of the initial value (≈100 F g -1 ) after 10 000 cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

High Areal Energy 3D-Interdigitated Micro-Supercapacitors in Aqueous and Ionic Liquid Electrolytes

The fabrication of high performance on-chip 3D micro-supercapacitors (MSCs) based on MnO 2 pseudocapacitive binder-free thin film electrodes (< 500 nm thick) with interdigitated topology is reported. An original technological process easily scalable to pilot production line is proposed on 3-inch silicon wafers. High areal energy (> 10 μWh.cm -2 ) and power densities (> 10 mW.cm -2 ) are reached on small footprint micro-supercapacitors (4 mm 2 ) tested in aqueous electrolyte (0.8 V). Furthermore, the cell voltage of such MSC can be increased up to 1.5 V with EMI TFSI ionic liquids but at the expense of the areal capacitance. The performance in ionic liquid is in the same order of magnitude than the one obtained for aqueous electrolyte. The benefit from the 3D topology is clearly demonstrated when the surface performance are normalized to the electrode thickness allowing to obtain an interesting energy vs power tradeoff (> 10 μWh.cm -2 μm -1 and > 1 mw.cm -2 μm -1 ). Here, this paper aims at improving the energy density of MSCs while keeping high power capability, by combining the use of ionic liquids and the deposition of MnO 2 thin film onto robust and efficient 3D scaffolds.

3D silicon microtubes↗
DOE OSTI2019

Energy Storage Data Reporting in Perspective—Guidelines for Interpreting the Performance of Electrochemical Energy Storage Systems

Due to the tremendous importance of electrochemical energy storage, numerous new materials and electrode architectures for batteries and supercapacitors have emerged in recent years. Correctly characterizing these systems requires considerable time, effort, and experience to ensure proper metrics are reported. Many new nanomaterials show electrochemical behavior somewhere in between conventional double-layer capacitor and battery electrode materials, making their characterization a non-straightforward task. It is understandable that some researchers may be misinformed about how to rigorously characterize their materials and devices, which can result in inflation of their reported data. Additionally, this is not uncommon considering the current state of the field nearly requires record breaking performance for publication in high-impact journals. Incorrect characterization and data reporting misleads both the materials and device development communities, and it is the shared responsibility of the community to follow rigorous reporting methodologies to ensure published results are reliable to ensure constructive progress. This tutorial aims to clarify the main causes of inaccurate data reporting and to give examples of how researchers should proceed. The best practices for measuring and reporting metrics such as capacitance, capacity, coulombic and energy efficiencies, electrochemical impedance, and the energy and power densities of capacitive and pseudocapacitive materials are discussed.

25 ENERGY STORAGE↗
DOE OSTI2019

Tuning the Electrochemical Performance of Titanium Carbide MXene by Controllable In Situ Anodic Oxidation

MXenes are a class of two-dimensional (2D) transition metal carbides, nitrides and carbonitrides that have shown promise for high-rate pseudocapacitive energy storage. However, the effects that irreversible oxidation have on the surface chemistry and electrochemical properties of MXenes are still not understood. In this work, we report on a controlled anodic oxidation method which improves the rate performance of titanium carbide MXene (Ti 3 C 2 T x , T x refers to -F, =O, -Cl and -OH) electrodes in acidic electrolytes. The capacitance retention at 2000 mV s -1 (with respect to the lowest scan rate of 5 mV s -1 ) increases gradually from 38% to 66% by tuning the degree of anodic oxidation. At the same time, a loss in the redox behavior of Ti 3 C 2 T x is evident at high anodic potentials after oxidation. Several analysis methods are employed to reveal changes in the structure and surface chemistry while simultaneously introducing defects, without compromising electrochemically active sites, are key factors for improving the rate performance of Ti 3 C 2 T x . This study demonstrates improvement of the electrochemical performance of MXene electrodes by performing a controlled anodic oxidation.

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

Dual-Ion Intercalation and High Volumetric Capacitance in a Two-Dimensional Non-Porous Coordination Polymer

Intercalation is a promising ion-sorption mechanism for enhancing the energy density of electrochemical capacitors (ECs) because it offers enhanced access to the electrochemical surface area. It requires a rapid transport of ions in and out of a host material, and it must occur without phase transformations. Materials that fulfil these requirements are rare; those that do intercalate almost exclusively cations. Herein, we show that Ni3(benzenehexathiol) (Ni 3 BHT), a non-porous two-dimensional (2D) layered coordination polymer (CP), intercalates both cations and anions with a variety of charges. Whereas cation intercalation is pseudocapacitive, anions intercalate in a purely capacitive fashion. The excellent EC performance of Ni3BHT provides a general basis for investigating similar dual-ion intercalation mechanisms in the large family of non-porous 2D CPs.

36 MATERIALS SCIENCE↗