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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Multiscale Understanding of Surface Structural Effects on High-Temperature Operational Resiliency of Layered Oxide Cathodes

The worldwide energy demand in electric vehicles and the increasing global temperature have called for development of high-energy and long-life lithium-ion batteries (LIBs) with improved high temperature operational resiliency. However, current attention has been mostly focused on cycling aging at elevated temperature, leaving considerable gaps of knowledge in the failure mechanism and practical control of abusive calendar aging and thermal runaway that are highly related to the eventual operational lifetime and safety performance of LIBs. Herein, using a combination of various in situ synchrotron X-ray and electron microscopy techniques, we report a multiscale understanding of surface structure effects involved in regulating the high temperature operational tolerance of polycrystalline Ni-rich layered cathodes. Our results collectively show that an ultraconformal poly (3,4-ethylenedioxythiophene) coating can effectively prevent LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode from undesired phase transformation and transition metal dissolution on the surface, atomic displacement and dislocations within primary particles, intergranular cracking along the grain boundaries within secondary particles, and intensive bulk oxygen release during high state-of-charge and high temperature aging. As a result, the present work highlights the essential role of surface structure controls in overcoming the multiscale degradation pathways of high-energy battery materials at extreme temperature.

25 ENERGY STORAGE↗
DOE OSTI2024

Cost‐Effective Layered Oxide – Olivine Blend Cathodes for High‐Rate Pulse Power Lithium‐Ion Batteries

Abstract Sustainability and supply‐chain concerns require lithium‐ion batteries (LIBs) free from critical minerals, such as nickel and cobalt. While recent advances provide encouraging signs that cobalt can be removed, the question remains how much Ni can be removed from Co‐free layered oxide cathodes before sacrificing critical performance metrics. This study highlights the effect of reducing Ni by benchmarking several Co‐free cathodes with decreasing Ni content. Keeping the energy density the same by increasing the charge voltage, cathodes below 80% Ni content exhibit worsened capacity fade due to increasing oxygen release and electrolyte decomposition. Charge transfer and diffusion kinetics are also hindered with increasing Mn content and exacerbated by resistive surface phases formed at high voltages, rendering lower‐Ni, Co‐free cathodes less competitive than high‐Ni cathodes for high energy and power applications. It is demonstrated blending layered oxide with olivine as an effective alternative to deliver energy density and cycling stability comparable to lower‐Ni cathodes with moderate charging voltages. Blending with 30 wt% olivine LiMn 0.5 Fe 0.5 PO 4 (LMFP) virtually eliminates the diffusion limitation of layered oxides at low state‐of‐charge, with enhanced pulse power characteristics rivaling the high‐Ni counterparts. Cathode blending can further reduce the overall Ni content and cost without the performance limitations of lower‐Ni, Co‐free cathodes.

Lee, Steven↗
DOE OSTI2023

High‐Nickel Heterostructured Cathodes with Local Stoichiometry Control for High‐Voltage Operation

The growing demand for lithium‐ion batteries to power electric vehicles and other energy‐dense devices continues to fuel the need for cathodes of increasingly higher nickel in cathodes. The relentless pursuit of high Ni content, however, raises concerns on compromising cell lifetime and safety, especially under high‐voltage operation. Alternative to the traditional design of uniform or core–shell composition, we report a rational control of local stoichiometry in high‐Ni cathodes, enabling their high thermal and cycling stabilities—up to 258 °C at the fully charged state and 91.4% capacity retention for 100 cycles between 2.7 and 4.4 V. Multimodal synchrotron X‐ray characterization unveils the heterostructure of secondary particles, featuring a high‐Ni core (LiNi 0.90 Mn 0.05 Co 0.05 O 2 ) covered by a thin Ni‐gradient layer that remains stable over prolonged cycling due to suppressed oxygen release and structural deterioration. This work underlines, the intricate interplay between local stoichiometry and redox reactions in stabilizing high‐Ni cathodes for high‐voltage operation while ensuring safety.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Thermochemical reduction modeling in a high-temperature moving-bed reactor for energy storage: 1D model

The design of robust and efficient high-temperature thermochemical reactors and determination of operating conditions are critical steps toward enabling high-efficiency long-duration solar energy storage. This work presents a computational model for the thermal reduction of a metal oxide material (Mg-Mn-O) up to 1450 °C and the coupled complex transport phenomena in a novel tubular thermal reactor design that features the capability for a high extent-of-reduction (high energy storage density) and inherent heat recuperation. A one-dimensional model coupling counter-current gas–solid flow, two-phase heat transfer, thermochemical redox reactions, and species transport in a moving-bed reactor is developed. Simplified versions of the model are validated with published results in the literature for packed beds with both inert and reactive particles; the fully coupled model is also validated with experimental measurements of a moving-bed reactor in terms of local temperatures and oxygen release at the exit. Detailed comparisons on the effects of different boundary conditions in the reaction zone (prescribed wall temperature vs. heat flux conditions) and formulations based on a simple uniform flow assumption vs. plug flow using Ergun equation for gas flow are investigated. The results are compared with experimental measurements, and for all cases, the energy flow components in the reactor system and the thermal to chemical conversion efficiency and overall system efficiency are computed. Finally, the predicted high thermal-to-chemical efficiency ~95% and system efficiency ~30% agree with experimental measurements.

25 ENERGY STORAGE↗
DOE OSTI2022

Revisiting the capacity-fading mechanism of P2-type sodium layered oxide cathode materials during high-voltage cycling

We report P2-type sodium layered oxide cathode (Na 2/3 Ni 1/3 Mn 2/3 O 2 , P2-NNMO) has attracted great attention as a promising cathode material for sodium ion batteries because of its high specific capacity. However, this material suffers from a rapid capacity fade during high-voltage cycling. Several mechanisms have been proposed to explain the capacity fade, including intragranular fracture caused by the P2-O2 phase transion, surface structural change, and irreversible lattice oxygen release. Here we systematically investigated the morphological, structural, and chemical changes of P2-NNMO during high-voltage cycling using a variety of characterization techniques. It was found that the lattice distortion and crystal-plane buckling induced by the P2-O2 phase transition slowed down the Na-ion transport in the bulk and hindered the extraction of the Na ions. The sluggish kinetics was the main reason in reducing the accessible capacity while other interfacial degradation mechanisms played minor roles. Our results not only enabled a more complete understanding of the capacity-fading mechanism of P2-NNMO but also revealed the underlying correlations between lattice doping and the moderately improved cycle performance.

25 ENERGY STORAGE↗
DOE OSTI2024

Unleashing the Potential of Fast Charging Batteries: Leveraging Anion Redox Chemistry in Ni- and Co-Free Cathodes

Designing Li-ion battery cathodes free from critical raw materials such as Co and Ni has a huge technological and societal impact. Though anion redox-based Li-rich oxide cathodes allow designing Co and Ni free cathode compositions, the Li-rich oxides witnessed voltage fade, voltage hysteresis, and irreversible oxygen release despite their high capacity. Conversely, anion redox through highly covalent chalcogenides (S/Se) is emerging due to the improved covalency between metal d and ligand p bands. Here, we investigate the tuning of multi-chalcogen (S/Se) p-band and redox-active metal d-band in a model Li-rich chalcogen composition Li 1.13 Ti 0.57 Fe 0.3 S 2-y Se y (y = 0 - 1) through in-depth electrochemical, X-ray spectroscopy, and DFT-based electronic structure investigations. Introducing the appropriate amount of Se p band character in anion redox sulfides increases interlayer distance and metal - ligand covalency without modifying the original crystal structure, promoting significant electrochemical reversibility through mixed anionic (Se 2- /Se n- , S 2- /S n- , wherein n<2) and cationic (Fe 2+ /Fe 3+ ) redox reactions. Here we show the detailed Fe, S, and Se redox contributions during Li insertion/extraction through X-ray Absorption (XAS) and Hard X-ray Photoemission Spectroscopy (HAXPES) measurements. The orbital tuning approach improves rate capability for more than 10 C charge-discharge rate, exhibiting more than 50% of its original capacity obtained at C/20 rate. The buffer cation in the lattice (Ti 4+ ) remains electrochemically inactive even after significant Se p-band introduction in the sulfide framework. Overall, this work takes advantage of multi-anion redox chemistry to uncover practically demanding fast charging-discharging characteristics in intercalation cathodes. The obtained knowledge of this design can be extended to other oxide and chalcogen cathodes for high performance Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Electronic Structure and Safety Insights into Prussian Blue Analog Cathode Behavior at Elevated Temperatures in Sodium-Ion Batteries

Prussian blue analogs (PBAs) represent promising cathode materials for sodium-ion batteries (SIBs) due to their high theoretical capacity, open framework structure, and use of earth-abundant elements. However, the high-temperature structural evolution, water content effects, and thermal safety of PBAs, particularly in charged states, remain poorly understood, hindering their practical deployment. Here, we investigate Na 2 Fe[Fe(CN) 6 ]·2H 2 O using thermogravimetric analysis (TGA), ex situ and in situ temperature-dependent X-ray absorption spectroscopy (XAS), and accelerated rate calorimetry (ARC). TGA and ex situ XAS confirm water loss between 150 and 200 °C, resulting in Fe 2+ oxidation, enhanced local symmetry, and uniform redox behavior that improves electrochemical performance. In situ XAS reveals irreversible structural changes above 240 °C, including ligand loss, Fe site distortion, and increased disorder, while ARC on charged electrodes shows minimal self-heating rates (<0.1 °C/min) up to 300 °C, indicating exceptional thermal stability without lattice oxygen release. These insights elucidate PBA thermal dynamics, demonstrating improved electrochemical performance of water-deficient PBAs and informing future material design and safety assessment for SIB applications.

batteries↗
DOE OSTI2025

Exploring the Electrochemical Stability Window of an All-Solid-State Composite Cathode via a Novel Operando Tender XPS Setup

All-solid-state batteries (ASSBs) have the potential to provide greater energy density than conventional batteries based on liquid electrolytes. Here, an operando ASSB cell setup for tender X-ray photoelectron spectroscopy (XPS) was developed, and the interface of a Ni-rich layered transition metal oxide cathode active material (CAM) and an Li 6 PS 5 Cl (LPSCl) solid electrolyte (SE) was evaluated during initial charge/discharge cycles. After validating the cell performance against a conventional pouch cell operated at high compression, intermittent galvanostatic cycling was performed, and XPS data were recorded as a function of state of charge (SOC). Upon the initial charge of the cell to ≈3.3 V Li , the LPSCl appears to decompose into LiCl, Li 3 PS 4 , and polysulfides, whose amount gradually increases with potential. Upon further charge, at a potential higher than ≈3.8 V Li , initially, present sulfate and sulfite impurities decompose, and at ≈74% SOC (corresponding to a cathode potential of ≈4.10 V Li ), surface reconstruction of the CAM particles due to lattice oxygen release is detected. In addition, at potentials beyond ≈4.6 V Li , a decrease of the S 1s counts of the sum of the LPSCl, the thiophosphate, and polysulfide species suggests the formation of elemental sulfur that is lost via sublimation into the vacuum chamber.

25 ENERGY STORAGE↗
DOE OSTI2024

Suppressing strain propagation in ultrahigh-Ni cathodes during fast charging via epitaxial entropy-assisted coating

Surface reconstruction and the associated severe strain propagation have long been reported as the major cause of cathode failure during fast charging and long-term cycling. Despite tremendous attempts, no known strategies can simultaneously address the electro-chemomechanical instability without sacrificing energy and power density. Here we report an epitaxial entropy-assisted coating strategy for ultrahigh-Ni LiNi x Co y Mn 1-x-y O 2 (x ≥ 0.9) cathodes via an oriented attachment-driven reaction between Wadsley-Roth phase-based oxides and the layered-oxide cathodes. Further, the high anti-cracking and anti-corrosion tolerances as well as the fast ionic transport of the entropy-assisted surface effectively improved the fast charging/discharging capability, wide temperature tolerance and thermal stability of the ultrahigh-Ni cathodes. Comprehensive analysis from the primary and secondary particle level to the electrode level using multi-scale in situ synchrotron X-ray probes reveals greatly reduced lattice dislocations, anisotropic lattice strain and oxygen release as well as improved bulk/local structural stability, even when charging beyond the threshold state of charge (75%) of layered cathodes. Layered Ni-rich oxide cathodes are susceptible to challenges with surface reconstruction and strain propagation, limiting their cyclability. The authors propose a solution involving oriented attachment-driven reactions, utilizing Wadsley-Roth nanocrystals and layered oxide to induce an epitaxial entropy-assisted coating, effectively addressing these issues.

25 ENERGY STORAGE↗
DOE OSTI2022

Different interfacial reactivity of lithium metal chloride electrolytes with high voltage cathodes determines solid-state battery performance

A deep understanding of the interaction of the surface of cathode materials with solid electrolytes is crucial to design advanced solid-state batteries (SSBs). This is especially true for the new class of lithium metal chloride (Li-M-Cl) solid electrolytes which are receiving rapidly growing attention due to their very high oxidative stability (>4 V) in combination with good ionic conductivity that can enable long cell cycle life. While Li-M-Cl electrolytes typically contain resource-limited metals (M) such as indium or rare earths, work has focused on substituting M with more abundant elements such as zirconium. Via operando resistance measurements using intermittent current interruption we explore the dynamic evolution of the interphase at the surface of Ni-rich NCM85 or NCM111 cathode particles inside a working SSB with three different Li-(M 1 ,M 2 )-Cl catholytes (Li 3 InCl 6 , Li 2 Sc 1/3 In 1/3 Cl 4 and Li 5/2 Y 1/2 Zr 1/2 Cl 6 ) to reveal the impact of the cationic metal substitution on the interfacial chemistry. We show that the metal plays a critical role in determining high voltage stability, contrary to prior assumptions. Using a combination of cyclic voltammetry and ultraviolet photoelectron spectroscopy measurements of the electronic band structure to assess oxidative stability; coupled with DFT calculations and ToF-SIMS to evaluate products formed at the interface at different upper cutoff potentials and degrees of delithiation, we are able to differentiate between electrochemical and chemical degradation. We find that Li 2 Sc 1/3 In 1/3 Cl 4 yields the highest (and Li 3 InCl 6 the lowest) stability against electrochemical oxidation, while Li 5/2 Y 1/2 Zr 1/2 Cl 6 undergoes a detrimental chemical reaction with oxygen released from Ni-rich NCM85 at high potentials, resulting in fast capacity fading. Altogether, our work establishes a platform for the metrics and an approach that can be utilized to efficiently evaluate the stability of new halide SEs in SSB cells.

25 ENERGY STORAGE↗
DOE OSTI2024

Accurately constituting robust interfaces for high-performance high-energy lithium metal batteries

High-energy lithium metal batteries (LMBs) have received ever-increasing interest. Among them, coupling lithium metal (Li) with nickel-rich material, LiNi x Mn y Co z O 2 (NMCs, x ≥ 0.6, x + y + z = 1), is promising because Li anodes enable an extremely high capacity (∼3860 mA h g −1 ) and the lowest redox potential (−3.04 V vs. standard hydrogen electrode), while NMCs can achieve a much higher capacity of ∼200 mA h g −1 and lower cost than those of LiCoO 2 . However, the resultant Li‖NMC cells have been hindered from commercialization due to a series of challenges related to the interface stability of both Li anodes and NMC cathodes. Specifically, Li anodes suffer from Li dendritic growth and the formation of solid electrolyte interphase (SEI), while NMC cathodes suffer from the formation of cathode electrolyte interphase (CEI) and other interface-related issues, including transition metal dissolution, oxygen release, cracking, and so on. To tackle these issues, recently, two sister techniques, atomic and molecular layer deposition (ALD and MLD), have emerged and exhibit tremendous capabilities to accurately constitute robust interfaces to achieve high-performance Li‖NMC LMBs. They can uniquely develop uniform and conformal films as surface coatings of LMBs in a precisely controllable mode at the atomic/molecular level, while proceeding with film deposition at low temperatures (e.g., ≤250 °C). In this Feature Article, we review the latest research progress in developing novel surface coatings via ALD and MLD for Li‖NMC LMBs and discuss outcomes for pursuing high performance.

25 ENERGY STORAGE↗
DOE OSTI2025

Enhancing the low-temperature performance of Pt-based three-way catalysts using CeO 2 (core)@ZrO 2 (shell) supports

Developing robust Pt/CeO 2 -based three-way catalysts (TWCs) with enhanced oxygen buffering capability and low-temperature activity is highly desirable. In this study, a new TWC family, Pt/(1 − x)CeO 2 (core)@xZrO 2 (shell) (where x = 0–0.5), was prepared and evaluated at degreened (DG) and hydrothermally aged (HTA) states. Incorporation of 0.1 molar concentration of ZrO 2 resulted in a decreased temperature that 50% (T 50 ) (CO: 167 °C, THCs: 218 °C, NO: 228 °C) and 90% (T 90 ) (CO: 207 °C, THCs: 237 °C, NO: 244 °C) conversions achieved over HTA 1.8 wt% Pt/0.9CeO 2 @0.1ZrO 2 compared to the HTA 1.8 wt% Pt/CeO 2 sphere (CO: T50,90 = 179, 222 °C, THCs: 234, 252 °C, NO x : 240, 260 °C). An enhanced oxygen storage capacity and oxygen release rate were observed over Pt/0.9CeO 2 @0.1ZrO 2 compared to the Pt/CeO 2 sphere. Increasing the ZrO 2 molar concentration to values greater than 0.2 resulted in increased T 50 s (224, 265 274 °C) and T 90 s (251, 289, 292 °C) for CO, THCs, and NO x , respectively, over 1.8 wt.% Pt/0.5CeO 2 @0.5ZrO 2 . Overall, this work highlights the potential of forming a ZrO 2 shell on CeO 2 spheres as a support for TWC applications.

Liu, Chih-Han [State Univ. of New York (SUNY), Buf↗
DOE OSTI2021

Precipitation of dopants on acceptor-doped LaMnO3±δ revealed by defect chemistry from first principles

Perovskite oxides degrade at elevated temperatures while precipitating dopant-rich particles on the surface. A knowledge-based improvement of surface stability requires a fundamental and quantitative understanding of the dopant precipitation mechanism on these materials. We propose that dopant precipitation is a consequence of the variation of dopant solubility between calcination and operating conditions in solid oxide fuel cells (SOFCs) and electrolyzer cells (SOECs). To study dopant precipitation, we use 20% (D = Ca, Sr, Ba)-doped LaMnO3+δ (LDM20) as a model system. We employ a defect model taking input from density functional theory calculations. The defect model considers the equilibration of LDM20 with a reservoir consisting of dopant oxide (DO), peroxide (DO2), and O2 in the gas phase. The equilibrated non-stoichiometry of the A-site and B-site as a function of temperature, T, and oxygen partial pressure, p(O2), reveals three regimes for LDM20: A-site deficient (oxidizing conditions), A-site rich (atmospheric conditions), and near-stoichiometric (reducing conditions). Assuming an initial A/B non-stoichiometry, we compute the dopant precipitation boundaries in a p–T phase diagram. Our model predicts precipitation both under reducing (DO) and under highly oxidizing conditions (DO2). We found precipitation under anodic, SOEC conditions to be promoted by large dopant size, while under cathodic, SOFC conditions precipitation is promoted by initial A-site excess. The main driving forces for precipitation are oxygen uptake by the condensed phase under oxidizing conditions and oxygen release assisted by B-site vacancies under reducing conditions. Possible strategies for mitigating dopant precipitation under in electrolytic and fuel cell conditions are discussed.

Hess, Franziska (ORCID:000000024460643X)↗
DOE OSTI2021

Plasma radiation behavior approaching high-radiation scenarios in W7-X

The W7-X stellarator has so far performed experiments under both limiter and divertor conditions. The plasma is mostly generated by ECR-heating with powers up to 6.5 MW, and the plasma density is usually limited by the radiation losses from low-Z impurities (such as carbon and oxygen) released mainly from the graphite targets. The present work first summarizes the radiation loss fractions f rad achieved in quasi-stationary hydrogen plasmas in both operational phases, and then shows how impurity radiation behaves differently with the two different boundary conditions as the plasma density increases. The divertor operation is emphasized and some beneficial effects (with respect to impurity radiation) are highlighted: (1) intensive radiation is located at the edge (r/a > 0.8) even at high radiation loss fractions, (2) the plasma remains stable up to f rad approaching unity, (3) the reduction in the stored energy is about 10% for high f rad scenarios. Moreover, effects of wall boronisation on impurity radiation profiles are also presented.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Improving the Long-term Cycle Performance of xLi 2 MnO 3 ·(1-x)LiMeO 2 /Li 4 Ti 5 O 12 Cells via Prelithiation and Electrolyte Engineering

Toward the development of high energy density and long lifetime batteries for behind-the-meter storage (BTMS) applications, Li- and Mn-rich layered oxide cathode (xLi 2 MnO 3 ·(1-x)LiMeO 2 , Me = Ni, Mn, and etc., LMR-NM) and Li 4 Ti 5 O 12 (LTO) anode system was examined. To mitigate the major degradation mechanisms at each electrode (i.e., loss of Li inventory (LLI) at the anode and transition metal dissolution and oxygen release at the cathode), two approaches were taken—prelithiating the LTO electrode and varying the electrolyte solvent compositions. The effect of prelithiation and electrolyte engineering on the long-term cycle performance of LMR-NM/LTO cells were systematically evaluated via electrochemical analyses and post-mortem characterizations. By using a prelithiated LTO anode and supplying additional Li to the system, the capacity retention of LMR-NM/LTO system was improved. The degree of enhancement was dependent on the types of electrolytes used, as their decomposition products determined the level of LLI. With increased capacity retention, however, the cathode was utilized to a greater extent, resulting in more severe loss of the cathode active material. Thus, all degradation mechanisms should be considered comprehensively when designing high performance LMR-NM/LTO cells to account for their complex interplay.

25 ENERGY STORAGE↗
DOE OSTI2024

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

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

25 ENERGY STORAGE↗
DOE OSTI2020

Safety Testing and Destructive Examination of AGR-2 UO 2 Compact 3-1-1

Post-irradiation examination and elevated-temperature safety testing are being performed on compacts from the Advanced Gas Reactor (AGR) Fuel Development and Qualification Program’s second irradiation experiment (AGR-2). The compacts in the AGR-2 irradiation experiment held either tristructural isotropic (TRISO)-coated particles containing uranium oxide fuel kernels (UO 2 ) or TRISO-coated particles containing fuel kernels with both uranium carbide and uranium oxide phases (UCO). In UO 2 TRISO particles, oxygen released by uranium fission can react with the surrounding carbon in the buffer layer to form carbon monoxide (CO). Excess CO can lead to various irradiation performance issues under certain operating conditions, such as pressure-induced fracture, kernel migration, and silicon carbide (SiC) corrosion. In UCO TRISO particles, CO formation is reduced because the chemical potential for oxidation of uranium carbide is lower than for oxidation of carbon.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗