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Mechanistic insights into low-temperature oxidation of carbon fibers: Influence of hydrogen defects and crystallite size
Although oxidation mechanisms have been exhaustively studied for graphite, similar analyses of carbon fibers are comparatively sparse. Most prior work has focused on quantifying weight loss or assessing protective surface coatings designed to slow oxidation. The use of optical spectroscopic techniques for oxidation analyses is comparatively unexplored, but such techniques could provide an early indicator of fiber oxidation that would undermine carbon fiber performance. Here, in this work, we applied Raman spectroscopy to study oxidation-induced spectral alterations in 16 carbon fiber types from 7 manufacturers oxidized at 300 °C for 72 h, 400 °C for 8 h, and 500 °C for 1 h. We connect these results with structural properties of the carbon fibers obtained through wide-angle X-ray scattering, identifying a linear dependence between the reactivity of carbon fibers and the crystallite size of the unperturbed fibers. We then demonstrate that substituted hydrogen defects are likely removed from the fiber surface during oxidation and use the relative defect concentration to predict the Raman spectral change as a function of temperature and time, assuming Arrhenius behavior.
Impact of Coal-Borne Impurities on Coal-Derived Graphene Quantum Dots
The goal is to develop a technological process for converting U.S. coals into high-value solid carbon products such as graphene and high-quality graphite.
Effect of chlorine purification on oxidation resistance of some mechanical carbons
Oxidation experiments were conducted with some experimental and commercial mechanical carbons at 650 C in dry air flowing at 28 cc/sec (STP). In general, purification of these carbon-graphites with chlorine at 2800 C improved oxidation resistance. Additional improvements in oxidation resistance were obtained from purification followed by an antioxidant (zinc phosphate) treatment. For the commercial materials, purification alone gave greater oxidation resistance than the antioxidant treatment alone. The reverse, however, was the case for the experimental materials.
Fast Charging of Li-Ion Cells: Part III. Relaxation Dynamics and Trap-Controlled Lithium Ion Transport
Fast charging of Li-ion batteries would ease consumer concerns regarding refueling time of electric vehicles. In this series of articles, we are systematically examining the effects of high currents flowing through the cell. Here we consider open-circuit relaxation dynamics for cell voltage and individual electrode potentials after abrupt termination of steady-state charging currents (1-6C) or short current pulses (< 30 s) of either polarity (to 16C). We demonstrate that dispersive kinetics observed after these current perturbations become faster for higher currents applied before the rest period. Our observations indicate that the voltage relaxation behaviors (i) depend on the current during charge, and less so on the state of charge, (ii) display universal stretched-exponential kinetics, (iii) can be induced by a short current pulse, (iv) require a minimum amount of charge transfer during the pulse, and (v) originate mainly from the oxide cathode. Trap controlled Li + ion transport through a partially disordered oxygen-depleted subsurface layer in the cathode is suggested as a possible origin for the relaxation behavior. The slow multidecadal responses to high currents can cause the nonlinearities observed during rapid charging of the electrochemical cells, reported in Part 2 of this series.
Investigation of the electrocatalytic oxygen reduction and evolution reactions in lithium–oxygen batteries
Oxygen reduction and oxygen evolution reactions were examined on graphite electrodes with different crystal orientations. The kinetics for the redox couple O 2 /O 2 •- are very fast, therefore no catalyst seems necessary to assist the charge transfer process. Apparently, the main source of the overpotential for the O 2 reduction reaction is from mass diffusion. Li 2 O 2 becomes soluble in non-aqueous electrolytes in the presence of the tetraethylammonium tetrafluoroborate additive. The soluble B-O 2 2- ions can be oxidized electro-catalytically. The edge orientation of graphite demonstrates superior catalytic activity for the oxidation over basal orientation. The findings reveal an opportunity for recharging Li-air batteries efficiently and a new strategy of developing the catalyst for oxygen evolution reaction.
PMR polyimide compositions for improved performance at 371 deg C
Studies were conducted to identify matrix resins which have potential for use at 371 C (700 F). Utilizing PMR methodology, neat resin moldings were prepared with various monomer reactants and screened for thermo-oxidative stability at 371 C (700 F) under both ambient and a four-atmosphere air pressure. The results of the resin screening studies indicate that high molecular weight (HMW) formulated resins of first (PMR-15) and second (PMR-II) generation PMR materials exhibit lower levels of weight loss at 371 C (700 F) than PMR-15 and PMR-II resins. The resin systems which exhibited the best overall balance of processability, Tg and thermo-oxidative stability at 371 C were used to prepare unidirectional Celion 6000 and T-40R graphite fiber laminates. Laminates were evaluated for thermo-oxidative stability and 371 C mechanical properties. Results of the laminate evaluation studies indicate that two of the resin compositions have potential for use in 371 C applications. The most promising resin composition provided laminates which exhibited no drop in 371 C mechanical properties and only 11 percent weight loss after 200 hr exposure to 4 atmospheres of air at 371 C.
PMR polyimide compositions for improved performance at 371 C
Studies were conducted to identify matrix resins which have potential for use at 371 C (700 F). Utilizing PMR methodology, neat resin moldings were prepared with various monomer reactants and screened for thermo-oxidative stability at 371 C (700 F) under both ambient and a four-atmosphere air pressure. The results of the resin screening studies indicate that high molecular weight (HMW) formulated resins of first (PMR-15) and second (PMR-II) generation PMR materials exhibit lower levels of weight loss at 371 C (700) than PMR-15 and PMR-II resins. The resin systems which exhibited the best overall balance of processability, Tg and thermo-oxidative stability at 371 C were used to prepare unidirectional Celion 6000 and T-40R graphite fiber laminates. Laminates were evaluated for thermo-oxidative stability and 371 C mechanical properties. Results of the laminate evaluation studies indicate that two of the resin compositions have potential for use in 371 C applications. The most promising resin composition provided laminates which exhibited no drop in 371 C mechanical properties and only 11 percent weight loss after 200 hr exposure to atmospheres of air at 371 C.
Through-thickness fracture behavior of neutron-irradiated nuclear graphite NBG-17 Using X-ray micro-CT
Achieving precise control over crack propagation in nuclear graphite and conducting quantitative analysis remain challenging. In this study, the through-thickness fracture behavior of pristine and neutron-irradiated (700 °C, ∼7 dpa) NBG-17 nuclear graphite was investigated using split-disc testing coupled with micro-computed tomography (micro-CT). A notably lower number of micropores was observed in the neutron-irradiated specimen. The fracture toughness of neutron-irradiated NBG-17 was measured to be 1.45 MPa√m, compared to 1.17 ± 0.05 MPa√m for the pristine specimen. In both materials, cracks were found to initiate at the filler–binder interface, and often correlated with microstructural features such as pores and thermal cracks. Crack bridging and deflections emerged as the primary toughening mechanisms in both unirradiated and irradiated NBG-17. However, compared with the pristine specimen, the cracks in the neutron-irradiated specimen were more likely to grow trans granularly, resulting in less deflected crack paths. The reduced micro-porosity and strengthened filler–binder boundaries were considered to be the cause of the observed differences in crack morphologies. In conclusion, this study provides a qualitative analysis of the fracture behavior of neutron-irradiated nuclear graphite in the absence of radiolytic oxidation.
Fabrication of Iron-Containing Carbon Materials From Graphite Fluoride
Carbon materials containing iron alloy, iron metal, iron oxide or iron halide were fabricated. Typical samples of these metals were estimated to contain 1 iron atom per 3.5 to 5 carbon atoms. Those carbon materials containing iron alloy, iron metal, and/or Fe3O4 were magnetic. The kinetics of the fabrication process were studied by exposing graphite fluoride (CF(0.68)) to FeCl3 over a 280 to 420 C temperature range. Between 280 and 295 C, FeCl3 quickly entered the structure of CF(0.68), broke the carbon-fluorine bonds, and within 10 to 30 min, completely converted it to carbon made up of graphite planes between which particles of crystalline FeF3 and noncrystalline FeCl3 were located. Longer reaction times (e.g., 28 hr) or higher reaction temperatures (e.g., 420 C) produced materials containing graphite, a FeCl3-graphite intercalation compound, FeCl2(center dot)4H2O, and FeCl2(center dot)2H2O. These products were further heat treated to produce iron-containing carbon materials. When the heating temperature was kept in the 750 to 850 C range, and the oxygen supply was kept at the optimum level, the iron halides in the carbon structure were converted to iron oxides. Raising the heat to temperatures higher than 900 C reduced such iron oxides to iron metal. The kinetics of these reactions were used to suggest processes for fabricating carbon materials containing iron alloy. Such processes were then tested experimentally. In one of the successful trial runs, commercially purchased CF(0.7) powder was used as the reactant, and NiO was added during the final heating to 1200 C as a source of both nickel and oxygen. The product thus obtained was magnetic and was confirmed to be a nickel-iron alloy in carbon.
Microstructural characterization of nuclear graphite: from the microscale to the nanoscale
Multiple reactor designs use graphite as a moderator of the nuclear reactions and as structural support. During the lifetime of the reactor, multiple aging factors such as neutron irradiation, oxidation, and temperature along with others induce changes in the microstructure and crystal lattice of graphite components. The pore morphology and crystal structure of some phases in graphite can be used to trace the evolution of irradiation defects and mechanical properties of graphite. We present a combination of results from several microscopy techniques to investigate the differences between nuclear graphite grades and the effects of neutron irradiation and oxidation at multiple length scales. This multiscale approach is needed to understand the microstructural variations caused by the raw materials and manufacturing processes as well as how the different phases of graphite are affected by the reactor environment. The results provide insight into the oxidation- and radiation-induced changes of graphite and create a robust baseline of microstructure information that can be used for the selection of materials for the next generation of nuclear power stations. Moreover, the experiments conducted in this work provide an overview of the advantages and limitations of the most common techniques used to characterize nuclear graphite and how these techniques might be applied to study other carbon-based materials used in the nuclear industry.
A Single Small-Scale Plutonium Redox Reaction System Yields Three Crystallographically-Characterizable Organoplutonium Complexes
Here, an approach to obtaining substantial amounts of data from a hazardous starting material that can only be obtained and handled in small quantities is demonstrated by the investigation of a single small-scale reaction of cyclooctatetraene, C 8 H 8 , with a solution obtained from the reduction of Cp' 3 Pu (Cp' = C 5 H 4 SiMe 3 ) with potassium graphite. This one reaction coupled with oxidation of a product has provided single-crystal X-ray structural data on three organoplutonium compounds as well as information on redox chemistry thereby demonstrating an efficient route to new reactivity and structural information on this highly radioactive element. The crystal structures were obtained from the reduction of C 8 H 8 by a putative Pu(II) complex, (Cp' 3 Pu II ) 1– , generated in situ, to form the Pu(III) cyclooctatetraenide complex, [K(crypt)][(C 8 H 8 ) 2 Pu III ], 1-Pu , and the tetra(cyclopentadienyl) Pu(III) complex, [K(crypt)][Cp' 4 Pu III ], 2-Pu . Oxidation of the sample of 1-Pu with Ag(I) afforded a third organoplutonium complex that has been structurally characterized for the first time, (C 8 H 8 ) 2 Pu IV , 3-Pu . Complexes 1-Pu and 3-Pu contain Pu sandwiched between parallel (C 8 H 8 ) 2– rings. The (Cp' 4 Pu III ) – anion in 2-Pu features three η 5 -Cp' rings and one η 1 -Cp' ring, which is a rare example of a formal Pu–C η 1 -bond. In addition, this study addresses the challenge of small-scale synthesis imparted by radiological and material availability of transuranium isotopes, in particular that of pure metal samples. A route to an anhydrous Pu(III) starting material from the more readily available Pu IV O 2 was developed to facilitate reproducible syntheses and allow complete spectroscopic analysis of 1-Pu and 2-Pu . Pu IV O 2 was converted to Pu III Br 3 (DME) 2 (DME = CH 3 OCH 2 CH 2 OCH 3 ) and subsequently Pu III Br 3 (THF) x , which was used to independently synthesize 1-Pu , 2-Pu , and 3-Pu .
Wide-Temperature Electrolytes for Lithium-Ion Batteries
Formulating electrolytes with solvents of low freezing points and high dielectric constants is a direct approach to extend the service temperature range of lithium (Li)-ion batteries (LIBs), for which propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl butyrate (MB) are excellent candidates. In this work, we report such low temperature electrolyte formulations by optimizing the content of ethylene carbonate (EC) in the EC-PC-EMC ternary solvent system with LiPF6 salt and CsPF6 additive. An extended service temperature range from 40°C to 60°C was obtained in LIBs with lithium nickel cobalt aluminum mixed oxide (LiNi0.80Co0.15Al0.05O2, NCA) as cathode and graphite as anode. The discharge capacities at low temperatures and the cycle life at room and elevated temperatures were systematically investigated in association with the ionic conductivity and phase transition behaviors. The most promising electrolyte formulation was identified as 1.0 M LiPF6 in EC-PC-EMC (1:1:8 by wt.) with 0.05 M CsPF6, which was demonstrated in both coin cells of graphite||NCA and 1 Ah pouch cells of graphite||LiNi1/3Mn1/3Co1/3O2. This optimized electrolyte enables excellent wide-temperature performances, as evidenced by the 68% capacity retention at 40C and C/5 rate, and nearly identical stable cycle life at room and elevated temperatures up to 60C.
Local measurement of bulk thermal diffusivity using photothermal radiometry
Here, an experimental methodology using photothermal radiometry is developed for the accurate measurement of bulk thermal diffusivity of nuclear fuels and materials irradiated to high doses. Under these conditions, nuclear fuels, such as uranium oxide, and moderator materials, such as graphite, become friable, which requires characterization techniques that can accommodate irregularly shaped fragments. Photothermal radiometry, a good candidate for this application, involves locally heating a sample by using a laser and measuring the temperature field by monitoring blackbody radiation. The interaction volume for this study, less than a millimeter, is carefully chosen to sample a statistically significant number of large-scale structural features, such as pores and gas filled bubbles, and is small enough that the sample fragments can be treated as a thermal half-space. The thermal diffusivity standards considered in this study cover a range of thermal diffusivities representative of both fresh and spent nuclear fuels. We also consider a sample having a porous microstructure representative of large-scale structures found in materials irradiated to high doses. Our measurement methodology circumvents complex thermal wave models that address optical diffraction, nonlinear transfer function associated with blackbody radiation, and finite sample size effects. Consequently, the large measurement uncertainty associated with modeling these effects can be avoided. While the emphasis here is on nuclear fuels and materials, this measurement approach is well suited to measure thermal transport in a variety of technologically important materials associated with advanced synthesis techniques. Examples range from small, exotic single crystals grown using hydrothermal growth techniques to additively manufactured components having complex geometries.
Spatially separating redox centers on 2D carbon nitride with cobalt single atom for photocatalytic H 2 O 2 production
Redox cocatalysts play crucial roles in photosynthetic reactions, yet simultaneous loading of oxidative and reductive cocatalysts often leads to enhanced charge recombination that is detrimental to photosynthesis. This study introduces an approach to simultaneously load two redox cocatalysts, atomically dispersed cobalt for improving oxidation activity and anthraquinone for improving reduction selectivity, onto graphitic carbon nitride (C 3 N 4 ) nanosheets for photocatalytic H 2 O 2 production. Spatial separation of oxidative and reductive cocatalysts was achieved on a two-dimensional (2D) photocatalyst, by coordinating cobalt single atom above the void center of C 3 N 4 and anchoring anthraquinone at the edges of C 3 N 4 nanosheets. Such spatial separation, experimentally confirmed and computationally simulated, was found to be critical for enhancing surface charge separation and achieving efficient H 2 O 2 production. This center/edge strategy for spatial separation of cocatalysts may be applied on other 2D photocatalysts that are increasingly studied in photosynthetic reactions.
Fast Charging of Li-Ion Cells: Part IV. Temperature Effects and “Safe Lines” to Avoid Lithium Plating
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Fast Charging of Li-Ion Cells: Part II. Nonlinear Contributions to Cell and Electrode Polarization
In this series, Li/Cu microprobes are used to monitor potentials of individual electrodes in situ during high-rate charging of Li-ion cells. Here we focus on capacity-limited charging of these cells to 6C, and present a general treatment of polarization that allows for data reduction and accurate interpolation/extrapolation over a wide range of charge rates. We show that the anode impedance as measured both using this new treatment and the more established pulsed-current techniques is not significantly changed after high-rate aging of the cell, including the conditions under which Li plating has occurred. Our measurements suggest that the changes in cell and electrode polarization to a large extent occur through nonlinear effects that involve time-delayed processes. An electrochemical model that includes phase dynamics in lithiated graphite is shown to capture some but not all of the observed trends suggesting that important facets of the high-rate behavior need to be included in such models.
Communication—Ligand-Dependent Electrochemical Activity for Mn 2+ in Lithium-Ion Electrolyte Solutions
Manganese dissolution from metal-oxide cathodes, and subsequent deposition at graphitic anodes, are considered to be key causes of capacity fade in lithium-ion batteries. The Mn2+ redox state is thought to be the major solvated Mn species, but its coordination environment is not well understood. Herein, we present the effects of Mn2+-containing electrolytes (Mn(PF6)(2) and Mn(TFSI)(2)) on the performance of lithium-iron-phosphate//graphite (LFP//Gr) cells. Clear differences in first-cycle capacities and subsequent cycling efficiencies depending on the associated counter-ion indicate that the Mn coordination environment has a profound effect on the associated electrochemical degradation mechanisms.