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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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324 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Activating Single‐Atom Ni Site via First‐Shell Si Modulation Boosts Oxygen Reduction Reaction

Abstract Atomically dispersed nitrogen‐coordinated 3d transition‐metal site on carbon support (M‐NC) are promising alternatives to Pt group metal‐based catalysts toward oxygen reduction reaction (ORR). However, despite the excellent activities of most of M‐NC catalysts, such as Fe‐NC, Co‐NC et al., their durability is far from satisfactory due to Fenton reaction. Herein, this work reports a novel Si‐doped Ni‐NC catalyst (Ni‐SiNC) that possesses high activity and excellent stability. X‐ray absorption fine structure and aberration‐corrected transmission electron microscopy uncover that the single‐atom Ni site is coordinated with one Si atom and three N atoms, constructing Ni‐Si 1 N 3 moiety. The Ni‐SiNC catalyst exhibits a half‐wave potential (E 1/2 ) of 0.866 V versus RHE, with a distinguished long‐term durability in alkaline media of only 10 mV negative shift in E 1/2 after 35 000 cycles, which is also validated in Zn‐air battery. Density functional theory calculations reveal that the Ni‐Si 1 N 3 moiety facilitates ORR kinetics through optimizing the adsorption of intermediates.

Chemistry↗
DOE OSTI2024

Sliceable, Moldable, and Highly Conductive Electrolytes for All-Solid-State Batteries

All-solid-state batteries (ASSBs) require solid electrolytes with high ionic conductivity, stability, and deformability for optimal energy and power density. Here, we developed lithium-deficient lithium yttrium bromide (LYB) solid electrolytes, Li 3–x YBr 6–x (0 ≤ x ≤ 0.50), using a comelting method with controlled lithium deficiency. These electrolytes exhibit favorable mechanical properties such as high moldability and sliceability. The Li 2.65 YBr 5.65 composition has an ionic conductivity of 4.49 mS cm –1 at 25 °C and an activation energy of 0.28 eV. Compared to Li 3 YBr 6 , Li 2.65 YBr 5.65 demonstrates improved rate performance and cycling stability in ASSBs. High-resolution X-ray diffraction confirms the formation of the LYB phase with a C2/m space group. Structural analysis reveals increased cation disorder and larger polyhedral volumes for x > 0 in Li 3–x YBr 6–x , contributing to reduced Li + migration energy barriers. Bond valence site energy calculations and molecular dynamics simulations reveal enhanced 3D lithium-ion transport. NMR spectroscopy further highlights increased Li + dynamics and impurity elimination.

Poudel, Tej P. [Florida State Univ., Tallahassee, ↗
DOE OSTI2023

Assessment of Modeling and Simulation Technical Gaps in Safety Analysis of High Burnup Accident-Tolerant Fuels

The United States nuclear industry is facing a strong challenge to maintain regulatory-required levels of safety while ensuring economic competitiveness to stay in business. Safety remains a key parameter for all aspects related to the operation of light water reactor (LWR) nuclear power plants (NPPs), and it can be achieved more economically by using a risk-informed ecosystem, such as that being developed by the Risk-Informed Systems Analysis (RISA) Pathway under the U.S. Department of Energy (DOE) Light Water Reactor Sustainability (LWRS) Program. The LWRS Program is promoting a wide range of research and development activities to maximize both the safety and economically efficient performance of NPPs through improved scientific understanding, especially given that many plants are considering second license renewal. The RISA Pathway has two main goals: The deployment of methodologies and technologies that enable better representation of safety margins and the factors that contribute to cost and safety, and; The development of advanced applications that enable cost-effective plant operation. As part of the RISA Pathway, the Enhanced Resilient Plant (ERP) project refers to an NPP where safety is improved by implementing various measures, such as accident-tolerant fuels (ATF), diverse and flexible coping strategy (FLEX), enhancements to plant components and systems, incorporation of augmented or new passive cooling systems, and utilization of advanced battery technologies. The objective of the ERP research is to use novel methods and computational tools to enhance existing reactors’ safety while reducing operational costs. Many U.S. utilities are targeting implementation of ATFs instead of traditional fuel in the near future since ATFs offer benefits in terms of improved performance and cost savings. The robust properties of ATF make it possible to extend the refueling cycle from 18 to 24 months in addition to the opportunity to use less of fuel. Extensive safety assessments are required to support regulatory requirements and obtain the approvals to use ATFs and the ERP project support the industry by developing novel effective methodologies for safety evaluations. In this project, the technical gaps in the modeling and simulation of the high burnup (HBU) ATF were assessed in terms of the fuel cladding behavior during the postulated accident events. The issues were identified in modeling the cladding deformation, the hydrodynamic change due to cladding deformation and the critical heat flux (CHF). The RELAP5-3D cladding deformation model was assessed by multiple verification tests and validation with the instrumented fuel assembly (IFA) experiment.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Field Validation of MVA Technology for Offshore CCS: Novel Ultra-High-Resolution 3D Marine Seismic Technology (P-Cable) (Final Report)

The objectives of the proposed study were to deploy and validate a specific monitoring technology, high-resolution 3D marine seismic (HR3D), appropriate for large-demonstration and commercial-scale offshore CCS sites. The project accomplished successful acquisition two HR3D seismic surveys. The first HR3D dataset was over the offshore injection site of the Tomakomai, Japan integrated pilot CCS project, which at the time of survey acquisition was actively injecting CO 2 . The first survey also represented a successful international collaboration between the DOE NETL program and Japan’s national CCS program and was the first successful acquisition and use of HR3D over an active CO 2 injection site (Meckel, Feng et al. 2019). The Tomakomai HR3D survey successfully tested a novel 4-streamer HR3D system array in which, for the first time, no cross-cable (aka “P-Cable”) was utilized and only four GeoEel streamers were used instead of the standard 12-streamer configuration. Consequently, this was not, strictly speaking, a deployment of the “P-Cable” system of (Planke and Berndt 2004) but rather a modified version, thereof, and it is the first known demonstration of the modified system configuration. One very positive outcome from the Japanese collaboration earlier in the project was the ability to learn from the Japanese how they used tail buoys with GPS to determine the position of the seismic source and receivers in time and space. Based on that experience, GCCC designed and built six GPS receivers that could be used to position the streamer receivers and the seismic source via tail buoys. A fundamental advance that was made on the original design, was the ability to directly power the tail buoy GPS units and transfer data through the streamers (i.e., vs. the batteries used at Tomakomai). The bulkiness of the GPS batteries caused drag and episodic surging of the buoys, which affected data quality by lifting up the tail end of the streamers so the receivers were not at the same depth. The units were tested onshore for accuracy and functionality, and the design was subsequently and successfully tested in marine acquisition mode during the SLP survey acquisition. The marine acquisition test and survey satisfied Subtasks 2.2.2, Novel Positioning Technology Selection and Subtask 2.2.3, Novel Positioning Technology Deployment. Results of the novel positioning technology selection (Subtask 2.2.2) were considered successful and will be incorporated in future HR3D seismic acquisition projects to reduce costs, improve deployment safety at sea, and integrate both seismic and data recording via a single data transfer through the streamers to the recording system. The project also established a permitting process through NETL NEPA compliance, which included an Environmental Assessment in a marine setting and is required for conducting these types of surveys using Federal funding. The permitting process charted a “boilerplate,” which can allow future surveys related to other funded projects to move forward more expeditiously. Future improvements that could be considered are more robust seals on the GPS module and stronger materials (especially joints) on tail buoy fabrication. These would increase fixed costs, but would be advisable and probably more economic long-term if multiple HR3D surveys are planned. Project Accomplishments include: • Pre-survey Sensitivity Study • Marine geochemistry methods and data analysis • Successful HR3D seismic dataset acquired @ Tomakomai active CO 2 injection marine site • Developed advanced seismic processing techniques • No NRMS anomalies detected in overburden; Demonstration of containment • Repeatability study • Second survey collected @ San Luis Pass, TX • 4D application using positioning techniques developed in the project for monitoring were successful

3D seismic GPS positioning↗
DOE OSTI2023

Influence of Potassium Metal-Support Interactions on Dendrite Growth

We report combined synchrotron X-ray nanotomography imaging, cryogenic electron microscopy (cryo-EM) and modeling elucidate how potassium (K) metal-support energetics influence electrodeposit microstructure. Three model supports are employed: O-functionalized carbon cloth (potassiophilic, fully-wetted), non-functionalized cloth and Cu foil (potassiophobic, nonwetted). Nanotomography and focused ion beam (cryo-FIB) cross-sections yield complementary three-dimensional (3D) maps of cycled electrodeposits. Electrodeposit on potassiophobic support is a triphasic sponge, with fibrous dendrites covered by solid electrolyte interphase (SEI) and interspersed with nanopores (sub-10 nm to 100 nm scale). Lage cracks and voids are also a key feature. On potassiophilic support, the deposit is dense and pore-free, with uniform surface and SEI morphology. Mesoscale modeling captures the critical role of substrate-metal interaction on K metal film nucleation and growth, as well as the associated stress state.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Descriptor-Based Analysis of Atomic Layer Deposition Mechanisms on Spinel LiMn 2 O 4 Lithium-Ion Battery Cathodes

Protective coatings have been shown to effectively suppress Mn ion dissolution from the spinel LiMn 2 O 4 lithium-ion battery cathode by stabilizing the surface against undesired side reactions with the electrolyte. In spite of extensive study, however, there remains a lack of atomic-scale understanding of how such coatings are deposited, and no molecular-level descriptor to predict trends in deposition mechanisms has been identified. We have recently shown that Al 2 O 3 coatings grown by atomic layer deposition (ALD) with alternating trimethylaluminum (TMA) and water exposures exhibit submonolayer growth because of precursor decomposition on the lithium manganate spinel (LMO) surface during early ALD pulses. In the present work, we elucidate the underlying mechanisms of this Al 2 O 3 ALD process using density functional theory (DFT) calculations and X-ray photoelectron spectroscopy (XPS) experiments, and we introduce a generalized descriptor-based framework to understand the resulting trends across a spectrum of surface structures and functionalities. We demonstrate that all decomposition products, including CH 3 -aluminum adducts and dissociated CH 3 groups, are Lewis bases and are coordinated to oxygen atoms on the LMO surface, leading to charge transfer to Lewis acidic Mn 3d states. Inert-transfer XPS supports these theoretical predictions, showing an increase in near-surface Mn 3+ content following TMA exposure and shifts in C is spectra consistent with C-O bond formation. We extend the DFT studies to various low- and high-index LMO surface facets, as a proxy for tuning the Lewis acid-base interactions between surface-bound CH 3 * and near-surface Mn ions. The thermochemistry for TMA reactions on these chemically distinct LMO surfaces demonstrates that ALD is structure-sensitive and that there is higher reactivity for TMA decomposition and Al 2 O 3 nucleation near LMO steps and defects. Motivated by the Lewis basic character of the decomposition products, we introduce the oxygen vacancy formation energy as a descriptor for decomposition energetics, and we demonstrate that all energetics are correlated to this quantity through the number of electrons that are transferred along the reaction coordinate. Finally, based on these findings, we hypothesize that improved electrochemical cycling with only 1-2 ALD cycles may be due to selective passivation of defect sites on the LMO surface that are more susceptible to Mn dissolution, and we suggest that similar descriptor-based analyses could be useful for the study of other ALD coatings on oxide substrates.

25 ENERGY STORAGE↗
DOE OSTI2022

First-principles comparative study of Cr migration in O3 and O/P hybrid-phased NaCrO 2

In layered Na transition-metal (TM) oxides, TM migration usually occurs at highly charged states and severely deteriorates the capacity and reversibility. Meanwhile, the formation of hybrid phases with the intergrowth of octahedral (O-type) and prismatic (P-type) Na layers also takes place at highly charged states. These hybrid phases are often more stable than simple O3 or P3 stackings. However, little is known about the mechanism and impact of TM migration in these hybrid phases. In this work, a comparative first-principles study is performed to understand the connections between structural changes and Cr migration in layered O3 and hybrid-phased NaCrO 2 . After Cr migration, the hybrid-phased NaCrO 2 suffers from greater layer shrinkage than the O3 phase. Three factors affect the Cr migration energy E mig : the Na concentration, local 3D configurations, and 2D in-plane geometries. Low Na concentrations and certain local 3D configurations facilitate the Cr migration. The Cr migration barriers in both O3 and hybrid-phased NaCrO 2 are positively correlated with the Cr E mig . The Cr migration in 17 doped O3 and hybrid-phased NaCrO 2 is surveyed. In these doped NaCrO 2 , a more uniform distribution of the Cr–O bond lengths usually suggests suppressed Cr migration. Optimal dopants for suppressing Cr migration are identified by considering E mig for both Cr and the dopant. Finally, our comparative study on Cr migration in O3 and hybrid-phased NaCrO 2 reveals the significant role of hybrid-phased structures in the development of layered cathode materials.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Scalable GPS Data Logging To Support Advanced Fleet Analysis

This highlight details the key takeaways from a project that utilized NLR's Fleet Research, Energy Data, and Insights (FleetREDI) data analysis pipeline. National Laboratory of the Rockies researchers developed and demonstrated low-cost, open-source Arduino data loggers with 3D-printed cases that are compatible with global navigational systems and built with components available ubiquitously worldwide, enabling cost-effective collection and analysis of fleet operational data. Validated on an overseas transit bus fleet, NLR analysis showed that, with sufficient charging opportunities, 90% of observed duty cycles could be accomplished by electric buses with no modifications to operations.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2023

Constructing stable interface layer for boosting high-voltage cycling performance of single-crystal Ni-rich cathodes

Increasing demand for electric vehicles (EVs) worldwide and the requirements for environmental protection have greatly promoted the development of low-Co, Ni-rich layered cathodes due to their high energy density, reasonable cost, and less environmental pollution. Nevertheless, serious performance degradation and safety concerns resulting from structural/interfacial instability under high operating voltages (≥4.3 V) have greatly hindered its commercialization. Herein, we propose a feasible surface modification strategy by introducing a multifunctional Li 2 SiO 3 (LSO) coating layer onto the surface of Co less single-crystalline LiNi 0.63 Co 0.07 Mn 0.3 O 2 (NCM) to solve the above challenges. Additionally, the uniform Li 2 SiO 3 coating layer has a unique three-dimensional (3D) ion diffusion channel, which greatly promotes the transmission of Li + and alleviates interfacial stress accumulation. Equally important, the electrochemically inert Li 2 SiO 3 coating layer has a stable structure framework with strong Si-O bonds, which inhibit anisotropic particle volume expansion and the occurrence of side reactions during long-term cycling. As a consequence, LSO modified NCM exhibits greatly improved electrochemical properties even at harsh testing conditions and achieves capacity retention of 79.1% after 200 cycles at 25°C within 2.95-4.5 V in half cells. Furthermore, it provides an outstanding capacity retention of 94.7% after 300 cycles at 25°C within 2.95-4.4 V when tested in pouch full cells.

25 ENERGY STORAGE↗
DOE OSTI2020

Exploring cycling induced crystallographic change in NMC with X-ray diffraction computed tomography

This study presents the application of X-ray diffraction computed tomography for the first time to analyze the crystal dimensions of LiNi 0.33 Mn 0.33 Co 0.33 O 2 electrodes cycled to 4.2 and 4.7 V in full cells with graphite as negative electrodes at 1 μm spatial resolution to determine the change in unit cell dimensions as a result of electrochemical cycling. The nature of the technique permits the spatial localization of the diffraction information in 3D and mapping of heterogeneities from the electrode to the particle level. An overall decrease of 0.4% and 0.6% was observed for the unit cell volume after 100 cycles for the electrodes cycled to 4.2 and 4.7 V. Additionally, focused ion beam-scanning electron microscope cross-sections indicate extensive particle cracking as a function of upper cut-off voltage, further confirming that severe cycling stresses exacerbate degradation. Finally, the technique facilitates the detection of parts of the electrode that have inhomogeneous lattice parameters that deviate from the bulk of the sample, further highlighting the effectiveness of the technique as a diagnostic tool, bridging the gap between crystal structure and electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2024

High–Performance NiCo 2 O 4 /Graphene Quantum Dots for Asymmetric and Symmetric Supercapacitors with Enhanced Energy Efficiency

For the sustainable growth of future generations, energy storage technologies like supercapacitors and batteries are becoming more and more common. However, reliable and high-performance materials’ design and development is the key for the widespread adoption of batteries and supercapacitors. Quantum dots with fascinating and unusual properties are expected to revolutionize future technologies. However, while the recent discovery of quantum dots honored with a Nobel prize in Chemistry, their benefits for the tenacious problem of energy are not realized yet. In this context, herein, chemical-composition tuning enabled exceptional performance of NiCo 2 O 4 (NCO)/graphene quantum dots (GQDs) is reported, which outperform the existing similar materials, in supercapacitors. A comprehensive study is performed on the synthesis, characterization, and electrochemical performance evaluation of highly functional NCO/GQDs in supercapacitors delivering enhanced energy efficiency. The high-performance, functional NCO/GQDs electrode materials are synthesized by the incorporation of GQDs into NCO. The effect of variable amount of GQDs on the energy performance characteristics of NCO/GQDs in supercapacitors is studied systematically. In-depth structural and chemical bonding analyses using X-ray diffraction (XRD) and Raman spectroscopic studies indicate that all the NCO/GQDs composites crystallize in the spinel cubic phase of NiCo 2 O 4 while graphene integration evident in all the NCO/GQDs. The scanning electron microscopy imaging analysis reveals homogeneously distributed spherical particles with a size distribution of 5–9 nm validating the formation of QDs. The high-resolution transmission electron microscopy analyses reveal that the NCOQDs are anchored on graphene sheets, which provide a high surface area of 42.27 m 2 g –1 and high mesoporosity for the composition of NCO/GQDs-10%. In addition to establishing reliable electrical connection to graphene sheets, the NCOQDs provide reliable 3D-conductive channels for rapid transport throughout the electrode as well as synergistic effects. Chemical-composition tuning, and optimization yields NCO/GQDs-10% to deliver the best specific capacitance of 3940 Fg –1 at 0.5 Ag –1 , where the electrodes retain ≈98% capacitance after 5000 cycles. The NCO/GQD-10%//AC asymmetric supercapacitor device demonstrates outstanding energy density and power density values of 118.04 Wh kg –1 and 798.76 W kg –1 , respectively. The NCO/GQDs-10%//NCO/GQDs-10% symmetric supercapacitor device delivers excellent energy and power density of 24.30 Wh kg –1 and 500 W kg –1 , respectively. These results demonstrate and conclude that NCO/GQDs are exceptional and prospective candidates for developing next-generation high-performance and sustainable energy storage devices.

25 ENERGY STORAGE↗
DOE OSTI2024

Reactive Carbon Capture: Cooperative and Bifunctional Adsorbent-Catalyst Materials and Process Integration for a New Carbon Economy

To say the least, releasing CO 2 into the atmosphere is reaping undue environmental consequences given the ever-present increase in severe global weather events over the past five years. However, it can be argued that–at least in the confines of current technological capabilities–the atmospheric release of CO 2 is somewhat unavoidable given that even shifting toward clean energy sources–such as solar, nuclear, wind, battery, or H 2 power–incurs an initial carbon requirement by way of manufacturing the very production abilities through which “clean” energy is generated. Even years from now, experts agree that energy production will be diversified and–as the global population continues to drive the growth of global energy consumption–thermal power derived from carbon combustion is likely to remain one intrinsic energetic source, of which CO 2 will always be a byproduct. In this context, it is the responsibility of the scientific community to devise improved pathways of carbon management such that (i) the consequences of combustion on the global environment are reduced and (ii) carbon fuels can be leveraged in a sustainable fashion. In this Account, we discuss a pivotal perspective shift on CO 2 emissions derived from a considerable breakthrough in material science from our work on shape engineering of nanoporous adsorbents and catalysts. This account details the development of materials which no longer vilify CO 2 emissions as a valueless combustion byproduct, instead providing a path for them to become a potential feedstock. In more specific terms, this work details the development of structured, cooperative “bifunctional” materials (BFMs) comprised of (i) a high-temperature adsorbent and (ii) a heterogeneous catalyst that enable single-bed CO 2 capture and utilization in oxidative ethane dehydrogenation (ODHE), oxidative propane dehydrogenation (ODHP), and dry methane reforming (DMR) processes. This Account begins with the conceptual development of the BFMs in the powdered state, followed by detailing the first-ever reports of structuring the materials into facile honeycomb contactors by 3D printing. The Account then summarizes the impressive performance of the 3D-printed BFMs, specifically focusing on how their catalysts (metal oxides and perovskites) influence their reactive CO 2 capture performances in ODHE, ODHP, and DMR processes. Such promise of CO 2 -as-fuel offers a glimpse into the future of a diversified energy economy, in which CO 2 /fuel looping can play an important role. A major factor in achieving this future is, of course, developing an appropriately active catalyst; an account of whose first breakthroughs in material science are detailed herein.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Pathway to High Rate Capability in Interconnected Composite Electrolytes: A Case Study with a Single-Ion-Conducting Polymer

In a three-dimensional interconnected polymer/ceramic composite electrolyte (3D composite), both the polymer and ceramic electrolyte phases are individually connected with a polymer-rich surface layer to provide conformal contact with the electrodes. This work investigates how the transference number of the polymer phase affects the electrochemical properties of the 3D composite. Here, we fabricate a 3D composite using a “single-ion” conducting polymer electrolyte (PE), Li 1+x+y Al x Ti 2–x Si y P 3–y O 12 (LICGC) ceramic, and compare its electrochemical properties with the neat polymer, and with a 3D composite made with a dual-ion-conducting PE (we reported previously). Our results reveal that changing the polymer phase from a dual-ion-conducting PE to a single-ion-conducting PE results in a 9-fold increase in the limiting current density, although the interfacial impedance between the polymer and LICGC ceramic remains high (and contributes significantly to the total impedance of the 3D composite). Further, the limiting current density of the 3D composite is dictated by the PE and minimally affected by the ceramic scaffold. The ceramic scaffold, however, helps to ease the concentration gradient buildup within the PE and moderately improves the overall transference number. The LICGC scaffold does not provide any additional Li dendrite resistance due to its high reactivity with Li.

25 ENERGY STORAGE↗
DOE OSTI2026

Thermodynamic Control of Interface Directs MnO 2 Nucleation Chemistry for Dense and Conformal Electrodeposition

Manganese dioxide (MnO 2 ) is widely recognized as a promising material for high-energy-density energy storage systems due to its broad applicability and facile electrodeposition. However, achieving uniform, thin, and high-mass-loading MnO 2 coatings on high-surface-area electrodes remains a significant challenge. Conventional electrodeposition methods typically yield nonuniform, thick layers with poor conductivity and limited material utilization, restricting their practical use. Here, we uncover a thermodynamically engineered vanadyl/pervanadyl (VO 2+ /VO 2 + ) interface that fundamentally reshapes MnO 2 electrodeposition chemistry, enabling highly uniform and dense coatings. Here, combining in situ AFM measurement, Classical Nucleation Theory, and Johnson–Mehl–Avrami–Kolmogorov modeling, we show that this interface reduces early-stage detectable MnO 2 island size by 35-fold and shifts the MnO 2 growth from diffusion-limited to reaction-limited progressive nucleation. This thermodynamically controlled interface yields highly dense and conformal MnO 2 films with record-high mass loading of 241 mg cm –2 (1607 mg cm –3 ) on 3D-printed graphene aerogels, without compromising porosity or inducing thickness gradient. As a prototype demonstration, the resulting MnO 2 electrodes deliver record-setting volumetric performance in both capacitors (106 F cm –3 ) and Zn//MnO 2 pouch cells (162 mAh cm –3 ). Beyond energy storage, our findings demonstrate the significance of thermodynamic interface control in MnO 2 nucleation chemistry for achieving dense and uniform coatings on various substrates, with implications for electrocatalysis, semiconductor processing, and advanced materials manufacturing.

Batteries↗
DOE OSTI2020

Petaloid-shaped ZnO coated carbon felt as a controllable host to construct hierarchical Li composite anode

Prestoring Li metal into the 3D host via thermal infusion strategy has been considered as an effective approach on suppressing Li dendrites growth of Li-metal anode during cycling. However, the fast Li infusing process generally induces uncontrollable and undesirable structures during the formation of composite Li metal anode. It is widely accepted that both physical and chemical interactions between the molten Li and the hosts provide driving forces for Li infusing into the host, but which one plays the dominant role has not been explored clearly. In this work, a 3D carbon felt coated by petaloid zinc oxide (CFZO) is designed as a controllable host for prestoring Li metal via thermal infusion method. It is revealed that the morphology induced physical driving force plays a more important role than the chemical reaction between ZnO and molten Li in the thermal infusion process. The physical driving force originates from the capillarity effect, depending on the roughness of the host according to Wenzel's model. An adjustable Li infusing process can be controlled to fabricate the Li composite electrode with a hierarchical structure (with dense Li-rich layer and porous Li-poor layer). The unique structure of the CFZO-Li not only provides enough spaces for Li deposition, but also disperses local current density to induce a uniform Li deposition behavior, thus Li dendrites can be suppressed effectively. As a result, CFZO-Li anode exhibits promising cycle stability when coupled with both Li-containing (LiNi 0.8 Co 0.15 Al 0.05 O 2 ) and Li-free (sulfur) cathodes.

25 ENERGY STORAGE↗
DOE OSTI2023

Laboratory-Scale Coal-Derived Graphene Process (Final Report)

The Energy & Environmental Research Center (EERC) conducted a laboratory-scale coal-derived graphene (CDG) project focused on developing a technological process for making graphene from four U.S. domestic coal or coal wastes, including lignite from North Dakota, subbituminous coal from Wyoming, bituminous coal from Utah, and anthracite from Pennsylvania. The project was divided into two performance or budget periods (BPs), with BP1 comprising the up-front laboratory experiments to make graphene materials from coal beginning on May 1, 2020, to April 30, 2022. BP2 was conducted from May 1, 2022, to April 30, 2023, and was focused on analyzing the CDG process economic feasibility and the technical gaps for technological scale-up and commercialization. During this project, a few different coal-derived high-value products have been demonstrated, including graphite, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs). A new graphite microstructure was discovered and named “croissant graphite” because of the exterior morphological and textural resemblance to croissant food items sold in commercial groceries stores. The new graphite structure and the associated preparation from coal or coal waste feedstocks has been the subject of a U.S. patent application. The systematic experimental processes involving coal cleaning, upgrading, and conversion to high-value carbon products culminated into a developed upgraded coal-to-products (UCP) technology that is being pursued for potential fast-track commercialization, if funding is available. It is envisioned that commercialization of the UCP technology would increase consumption of U.S. domestic coals or coal wastes to make environmentally sustainable high-value products for the electronics industry, high-energy-storage applications, and clean energy technologies such as electric vehicle (EV) lithium-ion batteries (LIBs), for which graphite has become a critical mineral commodity. Croissant graphite microstructures, when observed by field emission scanning electron microscopy (FESEM), display wavy surface morphology and often grow from a base that is made of graphitized particles with honeycomb-like layers, which are believed to be graphene layers. While more studies are needed to fully ascertain the mechanisms of the croissant graphite microstructure formation, it is postulated that their growth may begin from curling of the graphene sheets into ribbon-like structures, and continuous growth and densification of the ribbon-like structures forms croissant microstructures. Additional studies are ongoing to evaluate the electrochemical performance of croissant graphite for LIB applications and to determine the experimental conditions necessary to tune on/off croissant formation so that it can be either optimized or suppressed depending on performance evaluation results. In addition to the discovery of croissant graphite, the graphitization process from the four coal ranks in general was successful. X-ray diffraction (XRD) analysis showed that the degree of graphitization (DoG) ranged from 12% to 80% in an early sample set, and further optimization on lignite coal produces a DoG of about 92%, which was spectacular to see as lignite is the lowest-rank coal. Thus, it is expected that the graphitization performance for higher-rank coals will be similar or better when optimized as well. The coal-derived graphite was used to make GO and rGO. Analytical characterization, e.g., by methods such as Raman spectroscopy, XRD, Fourier transform infrared (FTIR) spectroscopy and FESEM, showed that the sequence of converting the coal to graphite, exfoliating it to GO, and then chemically reducing the GO to rGO was successful. Although coal naturally contains aromatic compounds and some relatively small-sized condensed aromatic units, it does not contain graphene sheets. In the UCP process, the aromatic domains in the coals, particularly low-rank coals, are concentrated and condensed further into graphene sheets, which are ordered into a 3D stack during graphitization. The synthesized graphite is then unpacked by methods such as exfoliation to various graphene products. GQDs were synthesized from all four coal types, and their optical properties were demonstrated to be tunable by the coal precursor preprocessing treatments. In all four coal types, enhanced optical properties were observed for the produced GDQs with incremental improvements made to the coal precursors. GQDs produced from raw coal samples displayed lower ultraviolet–visible (UV–Vis) spectroscopy absorbance intensity compared to those obtained from cleaned and upgraded coal residues. The photoluminescence (PL) intensities also varied with pretreatment conditions and with the concentration of GQDs in aqueous solutions. GQDs obtained from anthracite show longer emission wavelengths and can be excited by visible light as opposed to GQDs derived from the other coal ranks. UV fluorescence 3D maps and spectra revealed that the emission wavelength at which the GQDs solutions display the highest intensity was slightly redshifted based on the coal precursor pretreatments. In low-rank coal (lignite and subbituminous) samples, two clusters were observed in the maps for GQDs, which may suggest that there are potentially two types of fluorophores in solution or two main size populations. The ability to tune the properties of GQDs based on processing methods can be exploited to make GQDs for various optical display or optoelectronics applications. The results also highlight the importance of removing coal-borne impurities to improve the quality of the coal precursor for preparation of graphene products. Coal and/or coal wastes preprocessing methods were developed and applied to clean and upgrade the coal precursors prior to graphitization and subsequent conversion to graphene products. The preprocessing methods involve high specific-gravity separations, mineral acid cleaning (no hydrofluoric acid), and subsequent upgrading by reducing the coal-borne heteroatom (nitrogen, sulfur, and oxygen) content using proprietary chemical agents. Analytical characterization revealed that the preprocessing steps were successful, with ash reductions that range from 38% to 80% and residual ash content that was below the 5 wt% initial target. Based on proximate and ultimate analysis, the heteroatom reduction reactions produced upgraded coal residues with the oxygen content reduced by 8% to 24%, with additional reductions in the nitrogen and sulfur contents. An initial assessment of the waste streams from the UCP process shows very small to negligible environmental impact due to CO 2 , NO x , and SO x because most process steps are performed under inert atmosphere with argon. Consequently, reactive oxygen environments that tend to create these species are avoided. The inorganic and potentially hazardous species are released into aqueous waste streams that are easy to handle for proper disposal. The liquid waste streams were found to contain low-level concentrations of rare-earth elements (REEs), which could be concentrated and recovered as value-added by-products. Additionally, the volatile and gaseous fractions from carbonization and heat treatment contain useful organic compounds that can also be recovered as potential valuable by-products. Thus, the UCP technology is considered an environmentally sustainable and promising emerging technology for making high-value products from coal and coal wastes, with potential additional value-added by-products. Analysis of potential markets for the coal-derived carbon products shows a strong demand in both niche market sectors and across a wide variety of other industrial sectors. Graphite is currently considered a critical mineral commodity that has a large and growing demand in the LIB industry for EV applications. Based on data from Fortune Business Insights (2022) and Marketwatch (2023) reports, the average global graphite market is projected to reach about 33 billion by 2028, growing at a compound annual growth rate (CAGR) of about 7%, with much of this growth expected to be in the LIB industry. GO and rGO have strong market potentials in various application areas, such as coatings for anticorrosion, anti-icing, and antimicrobial protection, thermal barriers, wear resistance, sensors, additive manufacturing such as 3D inks, and others. GQDs are the emerging key player in the bioimaging, photovoltaics, and light-emitting diodes (LEDs) applications, with the potential to replace traditional semiconductor quantum dots (SQDs), which are based on metallic systems that are more toxic and more expensive. Biomedical applications of GQDs are becoming more attractive because of low to no toxicity and extremely low cost compared to SQDs. The major challenges for scale-up and commercialization of coal-derived carbon products such as graphene vary from the inherent attributes of graphene itself to reluctance to accept graphene in new manufacturing processes because of the uncertainty of the unknown. The 2D nature of graphene materials with a thickness of one atom presents significant challenges to proper handling/processing, and process scale-up becomes difficult because it requires high-end, expensive equipment, even for routine handling and analysis for quality assurance and control. Pristine graphene can also be extremely difficult to work into other matrices, thus hindering downstream processibility, especially at large scale. Currently, the cost of graphene and graphene products is still high and presents an economic risk that tends to slow down investment in scaling up emerging technologies. The lack of a standard for graphene materials for quality assurance and quality control poses a great challenge not only for the markets but also for commercialization efforts. A first-look economic feasibility analysis of the UCP technology provided valuable information that suggests the UCP process would be feasible, especially when it is scaled to a pilot scale and could be more competitive at the full scale. Graphitization was found to be the most energy-consuming and most capital-intensive step in the overall process. In small laboratory- and bench-scale experiments, labor is a significant contributor to the total process costs. Although these energy, capital, and labor constraints contribute to a higher selling price for the product, a preliminary economic model suggests that the process would be feasible at large scale when the process is fully integrated, optimized, and automated.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Revealing the aging process of solid electrolyte interphase on SiOx anode

Abstract As one of the most promising alternatives to graphite negative electrodes, silicon oxide (SiO x ) has been hindered by its fast capacity fading. Solid electrolyte interphase (SEI) aging on silicon SiO x has been recognized as the most critical yet least understood facet. Herein, leveraging 3D focused ion beam-scanning electron microscopy (FIB-SEM) tomographic imaging, we reveal an exceptionally characteristic SEI microstructure with an incompact inner region and a dense outer region, which overturns the prevailing belief that SEIs are homogeneous structure and reveals the SEI evolution process. Through combining nanoprobe and electron energy loss spectroscopy (EELS), it is also discovered that the electronic conductivity of thick SEI relies on the percolation network within composed of conductive agents (e.g., carbon black particles), which are embedded into the SEI upon its growth. Therefore, the free growth of SEI will gradually attenuate this electron percolation network, thereby causing capacity decay of SiO x . Based on these findings, a proof-of-concept strategy is adopted to mechanically restrict the SEI growth via applying a confining layer on top of the electrode. Through shedding light on the fundamental understanding of SEI aging for SiO x anodes, this work could potentially inspire viable improving strategies in the future.

25 ENERGY STORAGE↗
DOE OSTI2023

Role of Scaffold Architecture and Excess Surface Polymer Layers in a 3D-Interconnected Ceramic/Polymer Composite Electrolyte

3D-interconnected ceramic/polymer composite electrolytes offer promise to combine the benefits of both ceramic and polymer electrolytes. However, an in-depth understanding of the role of the ceramic scaffold's architecture, and the associated polymer/ceramic interfaces on the electrochemical properties of such composite electrolytes is still incomplete. Here, these factors are systematically evaluated using an interconnected composite electrolyte with a tunable and well-defined architecture. The ionic conductivity of the ceramic scaffold is strongly dependent on its porosity and tortuosity, as demonstrated experimentally and via theoretical modeling. The connectivity of the ceramic framework avoids the high interfacial impedance at the polymer/ceramic electrolyte interface within the composite. However, this work discovers that the interfacial impedance between the bulk composite and excess surface polymer layers of the composite membrane dominates the overall impedance, resulting in a 1–2 order drop of ionic conductivity compared to the ceramic scaffold. Despite the high impedance interfaces, an improved Li + transference number is found compared to the neat polymer (0.29 vs 0.05), attributed to the ceramic phase's contributions toward ion transport. Further, this leads to flatter overpotentials in lithium symmetric cell cycling. These results are expected to guide future research directions toward scalable manufacturing of composite electrolytes with optimized architecture and interfaces.

25 ENERGY STORAGE↗