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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Operando Analysis of Gas Evolution in TiNb 2 O 7 (TNO)-Based Anodes for Advanced High-Energy Lithium-Ion Batteries under Fast Charging

TiNb 2 O 7 (TNO) is regarded as one of the promising next-generation anode materials for lithium-ion batteries (LIBs) due to its high rate capabilities, higher theoretical capacity, and higher lithiation voltage. Furthermore, this enables the cycling of TNO-based anodes under extreme fast charging (XFC) conditions with a minimal risk of lithium plating compared to that of graphite anodes. Here, the gas evolution in real time with TNO-based pouch cells is first reported via operando mass spectrometry. The main gases are identified to be CO 2 , C 2 H 4 , and O 2 . A solid–electrolyte interphase is detected on TNO, which continues evolving, forming, and dissolving with the lithiation and delithiation of TNO. The gas evolution can be significantly reduced when a protective coating is applied on the TNO particles, reducing the CO 2 and C 2 H 4 evolution by ~2 and 5 times, respectively, at 0.1C in a half-cell configuration. The reduction on gas generation in full cells is even more pronounced. The surface coating also enables 20% improvement in capacity under XFC conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Synergy of Ion Doping and Spiral Array Architecture on Ti 2 Nb 10 O 29 : A New Way to Achieve High-Power Electrodes

Ameliorating electronic/ionic transport and structural stability of electrode materials is important to the development of power-intensive lithium ion batteries. Despite its great potential as a high-power anode, titanium niobium oxide (Ti 2 Nb 10 O 29 , TNO) still underperforms due to its unsatisfactory electronic/ionic conductivity. In this work, a powerful synergistic strategy by combining ion doping and spiral array architecture to boost high-rate performance of TNO is reported. Cr 3+ doped TNO nanoparticles (Cr-TNO) of 5-10 nm intimately grow on a conductive vertical graphene@TiC-C (VGTC) skeleton, forming novel Cr-TNO@VGTC spiral arrays. The unique spiral growth of TNO is achieved due to the confinement effect of VGTC skeleton. Meanwhile, a more open TNO crystal structure with faster ion transfer paths and enhanced structural stability is realized by Cr 3+ doping, demonstrated via density functional theory calculation and in situ synchrotron X-ray diffraction technique. Benefiting from the superior conductive network, enhanced intrinsic electronic/ionic conductivity of Cr-TNO and reinforced structural stability, the Cr-TNO@VTC arrays show prominent high-power performance with a large capacity of 220 mAh g -1 at 40 C (power density of ≈11 kW kg -1 ) and superior durability (91% retention after 500 cycles). This work provides a new path for the construction of widespread high-power electrodes for fast energy storage.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Mechanistic Insights into the Surface Instabilities of TiNb 2 O 7, a High‐Power Li‐Ion Anode

TiNb 2 O 7 (TNO) is a promising Li-ion battery anode for high-power applications, such as implantable medical devices and heavy-duty equipment. Hailed as being safe due to its elevated operating potential near 1.6 V, TNO has long been assumed to be highly stable in the carbonate-based electrolytes used in Li-ion batteries. Herein, all mechanisms occurring at the surface of both TNO and Nd-doped TNO are identified, and both materials in fact show significant gassing. CO 2 is even released at open circuit conditions, demonstrating the poor chemical stability of the material in the electrolyte even prior to battery operation. Such extreme instability is a critical safety concern. In addition, it was found that Ti dissolves from the surface of TNO particles at low voltage (below 1.4 V vs Li), and in fact deposits on the counter electrode. Ti further inside TNO particles then diffuses to the Ti-poor surface during discharge. Partial carbon-coating as a mitigating measure has also been tested and found to exacerbate these processes. The findings identify novel reactions occurring within TNO, and clearly highlight the need to stabilize the surfaces of TNO in order to prevent such aggressive deterioration at the surface of the particles.

25 ENERGY STORAGE↗
DOE OSTI2021

OSSOS. XXI. Collision Probabilities in the Edgeworth–Kuiper Belt

Here, we present results on the intrinsic collision probabilities, P {sub I}, and range of collision speeds, V {sub I}, as a function of the heliocentric distance, r, in the trans-Neptunian region. The collision speed is one of the parameters that serves as a proxy for a collisional outcome (e.g., disruption and scattering of fragments, or formation of a crater, as both processes are related to the impact energy). We utilize an improved and debiased model of the trans-Neptunian object (TNO) region from the “Outer Solar System Origins Survey” (OSSOS). It provides a well-defined model of TNO orbital distribution, based on multiple opposition observations of more than 1000 bodies. We compute collisional probabilities for the OSSOS models of the main classical, resonant, detached+outer, and scattering TNO populations. The intrinsic collision probabilities and collision speeds are computed using Öpik’s approach, as revised and modified by Wetherill for noncircular and inclined orbits. The calculations are carried out for each of the dynamical TNO groups, allowing for inter-population collisions as well as collisions within each TNO population, resulting in 28 combinations in total. Our results indicate that collisions in the trans-Neptunian region are possible over a wide range in (r, V {sub I}) phase space. Although collisions are calculated to happen within r ∼ 20–200 au and V {sub I} ∼ 0.1 km s{sup −1} to as high as V {sub I} ∼ 9 km s{sup −1}, most of the collisions are likely to happen at low relative velocities V {sub I} < 1 km s{sup −1} and are dominated by the main classical belt.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Titanium Niobium Oxide: From Discovery to Application in Fast-Charging Lithium-Ion Batteries

Lithium-ion batteries are essential for portable technology and are now poised to disrupt a century of combustion-based transportation. The electrification revolution could eliminate our reliance on fossil fuels and enable a clean energy future; advanced batteries would facilitate this transition. However, owing to the demanding performance, cost, and safety requirements, it is challenging to translate new materials from laboratory prototypes to industrial-scale products. This Perspective describes that journey for a new lithium-ion battery anode material, TiNb 2 O 7 (TNO). TNO is intended as an alternative to graphite or Li 4 Ti 5 O 12 with better rate and safety characteristics than the former and higher energy density than the latter. The high capacity of TNO stems from the multielectron redox of Nb 5+ to Nb 3+ , its operating voltage window well above the Li + /Li reduction potential prevents lithium dendrite formation, and its open crystal structure leads to high-power performance. Nevertheless, the creation of a practical TNO anode was nonlinear and nontrivial. Its history is built on 30 years of fundamental science that preceded its application as a battery anode, and its battery development included a nearly 30-year gap. The insights and lessons contained in this Perspective, many of them acquired firsthand, serve two purposes: (i) to unite the disparate studies of TiNb 2 O 7 into a coherent modern understanding relevant to its application as a battery material and (ii) to highlight briefly some of the challenges faced when scaling up a new material that affect TiNb 2 O 7 as well as new electrode candidates more generally.

25 ENERGY STORAGE↗
DOE OSTI2020

Translating a Material Discovery into a Commercial Product in the Modern Lithium-ion Battery Market

Lithium-ion batteries are essential for portable technology and are now poised to disrupt a century of combustion-based transportation. The electrification revolution could eliminate our reliance on fossil fuels and enable a clean energy future; advanced batteries would facilitate this transition. However, owing to the demanding performance, cost, and safety requirements, it is challenging to translate new materials from laboratory prototypes to commercial products. This Perspective describes that journey toward commercialization for a new lithium-ion battery anode material, TiNb2O7 (TNO). TNO is intended as an alternative to graphite or Li4Ti5O12 with better rate and safety characteristics than the former, and higher energy density than the latter. The high capacity of TNO stems from multielectron redox of Nb5+ to Nb3+, its operating voltage window well above Li+/Li reduction potential prevents lithium dendrite formation, and its open crystal structure leads to high-power performance. Nevertheless, the creation of a practical TNO anode was non-linear and non-trivial. Its history is built on 30 years on fundamental science that preceded its application as a battery, and its battery development included a nearly 30-year gap. The insights and lessons 2 contained in this Perspective, many of them acquired firsthand, serve two purposes: (i) to unite the disparate studies of TiNb2O7 into a coherent modern understanding relevant to its application as a battery material and (ii) to highlight some of the considerations of commercializing a new material that affect TiNb2O7 as well as new electrode candidates more generally.

Griffith, Kent J.↗
DOE OSTI2024

Community Solar Subscription Credit Considerations and Case Study

Together New Orleans (TNO) requested technical assistance through the US Department of Energy's (DOE's) National Community Solar Partnership (NCSP). The National Community Solar Partnership is a coalition of community solar stakeholders working to expand access to affordable community solar to every U.S. household and enable subscribers and their communities to realize meaningful benefits, such as reduced energy burden, increased resilience, community ownership, and equitable workforce development. TNO asked for a subject matter expert from NCSP to review the Entergy New Orleans (ENO) proposed revised Rate Schedule for Community Solar Generating Facilities. TNO requested that the proposed methodology for subscription credits for applicable residential and non-residential rate schedules be reviewed to determine the expected credit rate. The aim behind the analysis is to provide TNO and engaged stakeholders with an informed understanding of the proposed rate schedule before making decisions on the appropriate rate design for community solar (CS) subscriptions. This report is an exploration of CS subscription credit rate calculation considerations using the CS program in New Orleans as a case study. The report provides a framework for modeling CS credit rates in addition to topics that may be helpful to address when undertaking program design or rule making.

14 SOLAR ENERGY↗
DOE OSTI2020

Trans-Neptunian Objects Found in the First Four Years of the Dark Energy Survey

In this paper, we present a catalog of 316 trans-Neptunian bodies (TNOs) detected from the first four seasons ("Y4" data) of the Dark Energy Survey (DES). The survey covers a contiguous 5000 deg 2 of the southern sky in the grizY optical/NIR filter set, with a typical TNO in this part of the sky being targeted by 25–30 Y4 exposures. This paper focuses on the methods used to detect these objects from the ≈60,000 Y4 exposures, a process made challenging by the absence of the few-hour repeat observations employed by TNO-optimized surveys. Newly developed techniques include: transient/moving object detection by comparison of single-epoch catalogs to catalogs of "stacked" images; quantified astrometric error from atmospheric turbulence; new software for detecting TNO linkages in a temporally sparse transient catalog, and for estimating the rate of spurious linkages; use of faint stars to determine the detection efficiency versus magnitude in all exposures. Final validation of the reality of linked orbits uses a new "sub-threshold confirmation" test, wherein we demand the object be detectable in a stack of the exposures in which the orbit indicates an object should be present, but was not individually detected. This catalog contains all validated TNOs which were detected on ≥6 unique nights in the Y4 data, and is complete to r 23.3 mag with virtually no dependence on orbital properties for bound TNOs at distance 30 au < d < 2500 au. The catalog includes 245 discoveries by DES, 139 not previously published. The final DES TNO catalog is expected to yield >0.3 mag more depth, and arcs of >4 yr for nearly all detections.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
NASA NTRS2016

The Outer Solar System Origins Survey: Design and First-Quarter Discoveries - I.

We report the discovery, tracking, and detection circumstances for 85 trans-Neptunian objects (TNOs) from the first 42 square degrees of the Outer Solar System Origins Survey. This ongoing r-band solar system survey uses the 0.9 square degree field of view MegaPrime camera on the 3.6 meter Canada-France-Hawaii Telescope. Our orbital elements for these TNOs are precise to a fractional semimajor axis uncertainty of less than 0.1 percent. We achieve this precision in just two oppositions, as compared to the normal three to five oppositions, via a dense observing cadence and innovative astrometric technique. These discoveries are free of ephemeris bias, a first for large trans-Neptunian surveys. We also provide the necessary information to enable models of TNO orbital distributions to be tested against our TNO sample. We confirm the existence of a cold "kernel" of objects within the main cold classical Kuiper Belt and infer the existence of an extension of the "stirred" cold classical Kuiper Belt to at least several au beyond the 2:1 mean motion resonance with Neptune. We find that the population model of Petit et al. remains a plausible representation of the Kuiper Belt. The full survey, to be completed in 2017, will provide an exquisitely characterized sample of important resonant TNO populations, ideal for testing models of giant planet migration during the early history of the solar system.

Bannister, Michele T.↗
DOE OSTI2022

Research on high power, doped titanium-niobium oxide anodes

The main objective of this project is to synthesize titanium niobium oxide (TNO) that has a nanoporous structure with porous channels for rapid lithium diffusion, enabling extreme fast charging (XFC). The focus of this project is to improve the electronic conductivity and ion diffusion coefficient in TNO to achieve high capacities under extreme fast charge conditions. In addition, electrolytes with additives will be formulated to promote stable interphase formation on the NMC cathode surface to improve long cycling stability.

25 ENERGY STORAGE↗
DOE OSTI2024

Carbon Footprint Analysis of Floating PV Systems

This report, conducted by the Dutch research organization TNO, presents the first detailed life cycle inventory (LCI) analysis of operational floating photovoltaic (FPV) systems. The study, focusing on two operational systems in Western Europe, reveals that FPV systems on small inland water bodies can be a valuable complement to ground-mounted PV systems in terms of greenhouse gas emissions reduction. If PV module degradation is limited, these systems' carbon footprint is 3-4 times lower than the EU grid mix target for 2030. The report compares two FPV systems with different floater compositions (HDPE and steel/HDPE) to hypothetical ground-mounted systems, using comprehensive background data. The findings highlight the necessity for long-term monitoring and thorough environmental assessments. Josco Kester, a scientist at TNO, underscores the potential environmental benefits of these systems, which could enhance the adoption of renewable energy technologies.

14 SOLAR ENERGY↗
DOE OSTI2023

Photometry of Outer Solar System Objects from the Dark Energy Survey. I. Photometric Methods, Light-curve Distributions, and Trans-Neptunian Binaries

We report the methods of and initial scientific inferences from the extraction of precision photometric information for the >800 trans-Neptunian objects (TNOs) discovered in the images of the Dark Energy Survey (DES). Scene-modeling photometry is used to obtain shot-noise-limited flux measures for each exposure of each TNO, with background sources subtracted. Comparison of double-source fits to the pixel data with single-source fits are used to identify and characterize two binary TNO systems. A Markov Chain Monte Carlo method samples the joint likelihood of the intrinsic colors of each source as well as the amplitude of its flux variation, given the time series of multiband flux measurements and their uncertainties. A catalog of these colors and light-curve amplitudes A is included with this publication. We show how to assign a likelihood to the distribution q(A) of light-curve amplitudes in any subpopulation. Using this method, we find decisive evidence (i.e., evidence ratio <0.01) that cold classical (CC) TNOs with absolute magnitude 6 < H$_{r}$ < 8.2 are more variable than the hot classical (HC) population of the same H$_{r}$, reinforcing theories that the former form in situ and the latter arise from a different physical population. Resonant and scattering TNOs in this H$_{r}$ range have variability consistent with either the HCs or CCs. DES TNOs with H$_{r}$ < 6 are seen to be decisively less variable than higher-H$_{r}$ members of any dynamical group, as expected. More surprising is that detached TNOs are decisively less variable than scattering TNOs, which requires them to have distinct source regions or some subsequent differential processing.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
NASA NTRS2002

Formation and Migration of Trans-Neptunian Objects

We consider that trans-Neptunian objects (TNOs) with diameter d greater than 100 kilometers moving now in not very eccentric orbits could be formed directly by the compression of large rarefied dust condensations (with a greater than 30 AU), but not by the accretion of smaller solid planetesimals. Probably, some planetesimals with d approximately 100- 1000 kilometers in the feeding zone of the giant planets and even large main-belt asteroids also could be formed directly by such compression. Some smaller objects (TNOs, planetesimals, asteroids) could be debris of larger objects, and other such objects could be formed directly by compression of condensations. A small portion of planetesimals from the feeding zone of the giant planets that entered into the trans-Neptunian region could left in eccentrical orbits beyond Neptune and became so called "scattered objects". Our computer runs in which gravitational interactions of bodies were taken into account with the use of the spheres method, showed that the embryos of Uranus and Neptune could increase their semimajor axes from less than 10 AU to their present values, moving permanently in orbits with small eccentricities, due to gravitational interactions with the migrating planetesimals. Later on, Thommes et al. considered a similar model using direct numerical integration. The total amount of water delivered to the Earth during the formation of the giant, planets was about the mass of water in the Earth oceans. The end of such bombardment could be caused mainly by the planetesimals that became scattered objects. For the present mass of the trans-Neptunian belt, the collisional lifetime of 1-kilometer TNO is about the age of the Solar system, but only a small portion (less than 1%) of 100-km TNOs could be destroyed during this age. The probability of destruction of a typical TNO (with 30 less than a,less than 50 AU) by scattered objects can be of the same order of magnitude as that by typical TNOs. TNOs could be even more often destroyed during planet formation than during last 4 Gyr. The analysis of the results of the orbital evolution of Jupiter-crossing objects (JCOs) and TNOs showed that, in principle, the trans-Neptunian belt can provide up to 100% of Earth-crossing objects, but, of course, some of them came from the main asteroid belt. Most of the collisions of former JCOs with the Earth were from orbits with aphelia inside Jupiter's orbit and belonged to a small portion of objects which moved in such orbits for a long time. About 1 of 300 JCOs collided with the Sun. The ratio of the total mass of icy planetesimals that migrated from the feeding zone of the giant planets and collided with the planet to the mass of this planet was greater (by a factor of 3 in our runs) for Mars than that for Earth and Venus.

Ipatov, S. I.↗
NASA NTRS2008

Collisional Processing of Olivine and Pyroxene in Cometary Dust

According to the nebular theory of solar-system formation, collisions between bodies occurred frequently early in the solar system s history and continue at a lower rate even today. Collisions have reworked the surface compositions and structures of cometary nuclei, though to an unknown degree. The majority of the collisional history of a typical Jupiter-family comet takes place while it resides in the Kuiper Belt. Impacts occur on the surfaces of small bodies over a large range of velocities by impactors of all sizes, but typical encounter speeds within the Kuiper Belt are 1.5 to 2.0 km/s[1]. Durda and Stern suggest that the interiors of most cometary nuclei with diameters <5 km have been heavily damaged by collisions [2]. They estimate that over a period of 3.5 Gy, a nucleus with a diameter of 2 km and an orbit between 35-45 AU will experience 90-300 collisions with objects greater than 8 m in diameter. In this same time interval, collisions between a typical Trans-Neptunian Object (TNO) 200 km in diameter and objects with d > 8 m would rework up to one-third of that TNO s surface. In fact, it has been proposed that most short-period comets from the Kuiper Belt (90%) are collisional fragments from larger TNOs - not primordial objects themselves [3] - and that most short-period comets from the Kuiper Belt will be collisionally processed both on their surfaces as well as in their interiors.

Lederer, S. M.↗
NASA NTRS2014

Interstellar Organics, the Solar Nebula, and Saturn's Satellite Phoebe

The diffuse interstellar medium inventory of organic material (Pendleton et al. 1994, Pe 2002) was likely incorporated into the molecular cloud in which the solar nebula condensed. This provided the feedstock for the fo planets, and the smaller icy bodies in the region outside Neptune's orbit (transneptunian objects, or TNOs). Saturn's satellites Phoeb open a window to the composition of one class of TNO as revealed by the near-infrared mapping spectrometer (VIMS) on the Cass Phoebe (mean diameter 213 km) is a former TNO now orbiting Saturn. VIMS spectral maps of Phoebe's surface reveal a complex consisting of prominent aromatic (CH) and aliphatic hydrocarbon (CH2, CH3) absorption bands (3.2-3.6 μm). Phoebe is the source encircling Saturn, and from which particles (~5-20 μm size) spiral inward toward Saturn. They encounter Iapetus and Hyperion wh blanket the native H2O ice of those two bodies. Quantitative analysis of the hydrocarbon bands on Iapetus demonstrates that aroma abundant as aliphatic CH2+CH3, significantly exceeding the strength of the aromatic signature in interplanetary dust particles, com carbonaceous meteorites (Cruikshank et al. 2013). A similar excess of aromatics over aliphatics is seen in the qualitative analysis o itself (Dalle Ore et al. 2012). The Iapetus aliphatic hydrocarbons show CH2/CH3 ~4, which is larger than the value found in the di as Phoebe is a primitive body that formed in the outer regions of the solar nebula and has preserved some of the original nebula inv understanding the content and degree of processing of that nebular material. There are other Phoebe-like TNOs that are presently b in the organic spectral region, but JWST will open that possibility for a number of objects. We now need to explore and understand organic-bearing Solar System material to the solar nebula and the inventory of ISM materials incorporated therein.

Interstellar↗
NASA NTRS2014

Interstellar Organics, the Solar Nebula, and Saturn's Satellite Phoebe

The diffuse interstellar medium inventory of organic material (Pendleton et al. 1994, Pendleton & Allamandola 2002) was likely incorporated into the molecular cloud in which the solar nebula condensed. This provided the feedstock for the formation of the Sun, major planets, and the smaller icy bodies in the region outside Neptune's orbit (transneptunian objects, or TNOs). Saturn's satellites Phoebe, Iapetus, and Hyperion open a window to the composition of one class of TNO as revealed by the near-infrared mapping spectrometer (VIMS) on the Cassini spacecraft at Saturn. Phoebe (mean diameter 213 km) is a former TNO now orbiting Saurn. VIMS spaectral maps of PHoebe's surface reveal a complex organic spectral signature consisting of prominent aromatic (CH) and alophatic hydrocarbon (CH2, CH3) absorption bands (3.2-3.6 micrometers). Phoebe is the source of a huge debris ring encircling Saturn, and from which particles (approximately 5-20 micrometer size) spiral inward toward Saturn. They encounter Iapetus and Hperion where they mix with and blanket the native H2O ice of those two bodies. Quantitative analysis of the hydrocarbon bands on Iapetus demonstrates that aromatic CH is approximately 10 times as abundant as aliphatic CH2+CH3, significantly exceeding the strength of the aromatic signature in interplanetary dust particles, comet particles, ad in carbonaceous meteorites (Cruikshank et al. 2013). A similar excess of aromatics over aliphatics is seen in the qualitative analysis of Hyperion and Phoebe itself (Dalle Ore et al. 2012). The Iapetus aliphatic hydrocarbons show CH2/CH3 approximately 4, which is larger than the value found in the diffuse ISM (approximately 2-2.5). In so far as Phoebe is a primitive body that formed in the outer regions of the solar nebula and has preserved some of the original nebula inventory, it can be key to understanding the content and degree of procesing of the nebular material. There are other Phoebe-like TNOs that are presently beyond our ability to study in the organic spectral region, but JWST will open that possibility for a number of objects. We now need to explore and understand the connection of this organic-bearing Solar System material to the solar nebula the the inventory of ISM materials incorporated therein.

Interstellar↗