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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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This final technical report summarizes the findings of the University of Hawaiʻi and the National Renewable Energy Laboratory on the encapsulation of perovskite solar cells using novel polymers to enable extended operational lifetimes.
Composites demonstrating simultaneously enhanced-electrical conductivity, current density and lowered-temperature coefficient of resistance (TCR) compared to copper have been highly sought after for their advantages in efficient energy transport behavior. While such conductors have been demonstrated in 1D (nanowires) and 2D (films) samples, achieving similar behavior in 3D has been challenging owing to the limitations of the synthesis techniques used. In this paper, novel macro-scale 3D copper conductors were demonstrated with simultaneously increased electrical conductivity and decreased temperature coefficient of resistance (TCR) through the addition of graphene. Hot-extrusion was used to manufacture over 1-m-long, 2-mm-diameter copper-graphene composites with varying graphene content and defect density. Results showed that the electrical conductivity and current density in composites with low defect density graphene increased monotonically as a function of graphene content. They also demonstrated a significant decrease of over 17% in TCR with the addition of only 15 ppm graphene along with over 52% improvement in current density. Comparatively composites with high defect density graphene demonstrated lower electrical conductivity and current density. This study provides first-of-its-kind evidence of 3D metal composites whose bulk electrical performance has been enhanced using graphene additive in minute quantities. Further developments in this area are essential to achieve high performance composite conductors that can improve energy transport efficiency and pave way for industrial adoption of such materials in the future.
Na-β''-alumina (Na 2 O.~6Al 2 O 3 ) is known to be an excellent sodium ion conductor in battery and sensor applications. In this study we report fabrication of Na- β''-alumina + YSZ dual phase composite to mitigate moisture and CO 2 corrosion that otherwise can lead to degradation in pure Na-β''-alumina conductor. Subsequently, we heat-treated the samples in molten AgNO 3 and LiNO3 to respectively form Ag-β''-alumina + YSZ and Li-β''-alumina + YSZ to investigate their potential applications in silver- and lithium-ion solid state batteries. Ion exchange fronts were captured via SEM and EDS techniques. Their ionic conductivities were measured using electrochemical impedance spectroscopy. Both ion exchange rates and ionic conductivities of these composite ionic conductors were firstly reported here and measured as a function of ion exchange time and temperature.
Electrically conducting composites made from bromine-intercalated graphite fibers in epoxy matrix. Bromine-intercalated graphite fibers have conductivity of about 20,000 ohm-1cm-1 and found to be stable in presence of moisture fibers even submerged for indefinite times) and at reasonably high temperature (200 degrees C). Conventional epoxy resins can be used with such fibers. Composite materials containing 50 percent bromine-intercalated graphite fibers have promising properties. Mechanical properties of composites similar to composites made with pristine fibers: Tensile and flexural strengths and Young's and bending moduli essentially unchanged, and interlaminar shear strengths slightly enhanced. Thermal conductivities of composites also show very little degradation. However, electrical conductivities of composites increase, which invites application of composites in electrical grounding planes and in shields against electro-magnetic interference.
An innovative inorganic/polymer-composite encapsulation scheme comprising a polymer-based transparent conductive composite (TCC) coupled with a transparent conductive oxide is introduced to extend the lifetime of moisture-sensitive devices such as perovskite solar cells (PSC). The TCC comprises conductive silver-coated polymethyl methacrylate (Ag-PMMA) microsphere fillers protruding from a transparent non-conductive polymer matrix. TCC samples (5% Ag-PMMA by area) demonstrate high optical transparencies (%T approx. 85% in the 370–1200 nm region), low out-of-plane electrical resistivities (R < 0.2 Ω cm 2 ), and equilibrium permeabilities of less than 1 g mm/m 2 /day, all of which are well-maintained after 1,000 hours of environmental exposure. In practice, the TCC is employed between two indium zinc oxide (IZO) thin films, with the in-plane conductivity of IZO and the out-of-plane conductivity of TCC working collectively to function as a single encapsulating electrode. This encapsulation scheme is exemplified by benchmarking performances of PSCs subjected to accelerated aging conditions of quasi-maximum power point tracking under light soaking in air at 50 °C, 40% R.H. to 60% R.H. Notable improvements in operational lifetimes are observed, with a champion encapsulated PSC maintaining over 90% of its initial efficiency of 21.65% for up to 1,430 hours, compare to less than 300 hours for an unencapsulated control.
A thermal conductivity measuring apparatus that uses heat flow sensors to measure the heat flux through samples was constructed of inexpensive materials. This device was used to measure the thermal conductivity (k) of two composites used in the space program that consist of fibrous or granular components embedded in a resin matrix. The k-values that were determined ranged from 0.035 to 0.059 Btu/h sq ft-F/ft (-163 to 553 F) and 0.029 to 0.035 Btu/h-sq ft-F/ft (77 to 212 F). Thermal conductivity values of the composites conformed to the rule of mixture. The accuracy of the system was found to be comparable to the guarded hotplate and it requires neither a skilled operator nor extensive maintenance.
Polymer composites are being considered for numerous thermal applications because of their inherent benefits, such as light weight, corrosion resistance, and reduced cost. In this work, the microstructural, thermal, and mechanical properties of a 3D printed polymer composite with high thermal conductivity are examined using multiple characterization techniques. Infrared spectroscopy and X-ray diffraction reveal that the composite contains a polyphenylene sulfide matrix with graphitic fillers, which is responsible for the high thermal conductivity. Furthermore, differential scanning calorimetry determines that the glass transition and melting point of the composite are 87.6 °C and 285.6 °C, respectively. Thermogravimetric analysis reveals that the composite is thermally stable up to ~400 °C. Creep tests are performed at different isotherms to evaluate the long-term performance of the composite. The creep result indicates that the composite can maintain mechanical integrity when used below its glass transition temperature. Nanoindentation tests reveal that modulus and hardness of the composite is not significantly influenced by heating or creep conditions. These findings indicate that the composite is potentially suitable for heat exchanger applications.
Improved version of lead/sulfuric acid battery, electrically-conducting fiber/polymer composite substrates used in place of metallic substrates. Sealing and corrosion problems reduced. Benefits include halving of weight, increased energy and power densities, and lower gassing rate. Important for electric-vehicle development.
Gas derived graphite fibers generated by the decomposition of an organic gas are joined with a suitable binder. This produces a high thermal conductivity composite material which passively conducts heat from a source, such as a semiconductor, to a heat sink. The fibers may be intercalated. The intercalate can be halogen or halide salt, alkaline metal, or any other species which contributes to the electrical conductivity improvement of the graphite fiber. The fibers are bundled and joined with a suitable binder to form a high thermal conductivity composite material device. The heat transfer device may also be made of intercalated highly oriented pyrolytic graphite and machined, rather than made of fibers.
A solid ionically conductive composition (e.g., nanoparticles of less than 1 micron or a continuous film) comprising at least one element selected from alkali metal, alkaline earth metal, aluminum, zinc, copper, and silver in combination with at least two elements selected from oxygen, sulfur, silicon, phosphorus, nitrogen, boron, gallium, indium, tin, germanium, arsenic, antimony, bismuth, transition metals, and lanthanides. Also described is a battery comprising an anode, a cathode, and a solid electrolyte (corresponding to the above ionically conductive composition) in contact with or as part of the anode and/or cathode. Further described is a thermal (e.g., plasma-based) method of producing the ionically conductive composition. Further described is a method for using an additive manufacturing (AM) process to produce an object constructed of the ionically conductive composition by use of particles of the ionically conductive composition as a feed material in the AM process.
Enhancing transport and chemomechanical properties in cathode composites is crucial for the performance of solid-state batteries. Our study introduces the filler-aligned structured thick (FAST) electrode, which notably improves mechanical strength and ionic/electronic conductivity in solid composite cathodes. The FAST electrode incorporates vertically aligned nanoconducting carbon nanotubes within an ion-conducting polymer electrolyte, creating a low-tortuosity electron/ion transport path while strengthening the electrode’s structure. This design not only mitigates recrystallization of the polymer electrolyte but also establishes a densified local electric field distribution and accelerates the migration of lithium ions. The FAST electrode showcases outstanding electrochemical performance with lithium iron phosphate as the active material, achieving a high capacity of 148.2 milliampere hours per gram at 0.2 C over 100 cycles with substantial material loading (49.3 milligrams per square centimeter). This innovative electrode design marks a remarkable stride in addressing the challenges of solid-state lithium metal batteries.
Debonding of the fiber-matrix interface is a major cause for the degradation of the mechanical properties and the loss of thermal conductivity of fiber-reinforced composites. This paper discusses two analytical approaches for modeling the thermal conduction problem of composites. One is based on the concept of modeling the thermal barrier by an equivalent heat transfer coefficient at the fiber-matrix interface, as described by Hasselman and Johnson (1987) and Benveniste and Miloh (1986). The other approach, suggested by Hatta and Taya (1986), is by treating a composite with debonded interface as a coated-fiber composite. The major advantage of the latter aproach is that the thickness of the fiber coating can be realistically modeled depending upon the extent of degradation of the composite with the thermal conductivity of the coating as that of air.
The high-voltage LiNi 0.5 Mn 1.5 O 4 (LNMO) spinel cathode material offers high energy density storage capabilities without the use of costly Co that is prevalent in other Li-ion battery chemistries (e.g., LiNi x Mn y Co z O 2 (NMC)). Unfortunately, LNMO-containing batteries suffer from poor cycling performance because of the intrinsically coupled processes of electrolyte oxidation and transition metal dissolution that occurs at high voltage. In this work, we use operando electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies to demonstrate that transition metal dissolution in LNMO is tightly coupled to HF formation (and thus, electrolyte oxidation reactions as detected with operando and in situ solution NMR), indicative of an acid-driven disproportionation reaction that occurs during delithiation (i.e., battery charging). Leveraging the temporal resolution (s-min) of magnetic resonance, we find that the LNMO particles accelerate the rate of LiPF 6 decomposition and subsequent Mn 2+ dissolution, possibly due to the acidic nature of terminal Mn-OH groups. X-ray photoemission electron microscopy (XPEEM) provides surface-sensitive and localized X-ray absorption spectroscopy (XAS) measurements, in addition to X-ray photoelectron spectroscopy (XPS), that indicate disproportionation is enabled by surface reconstruction upon charging, which leads to surface Mn 3+ sites on the LNMO particle surface that can disproportionate into Mn 2+ (dissolved) and Mn 4+ (s) . During discharge of the battery, we observe high quantities of metal fluorides (in particular, MnF 2 ) in the cathode electrolyte interphase (CEI) on LNMO as well as the conductive carbon additives in the composite. Electronic conductivity measurements indicate that the MnF 2 decreases film conductivity by threefold compared to LiF, suggesting that this CEI component may impede both the ionic and electronic properties of the cathode. Ultimately, to prevent transition metal dissolution and the associated side reactions in spinel-type cathodes (particularly those that operate at high voltages like LNMO), the use of electrolytes that offer improved anodic stability and prevent acid byproducts will likely be necessary.
We reported that the incorporation of a conductive polymer into V 2 O 5 materials resulted in an increased interlayer distance of 2.2 nm, favoring K + ion storage in aqueous electrolyte. In situ X-ray diffraction showed that during charging, K + ions were first inserted into the interlayer region of V 2 O 5 through pseudocapacitive intercalation and then continued to be inserted into the [VO 6 ] bi-layer region via diffusion-limited intercalation. Furthermore, this reversible dual-stage insertion/extraction mechanism provides new battery chemistry allowing the storage of around 50% more alkali ions in the intralayer region besides van der Waals gaps.
Arrays of broadly responsive vapor detectors can be used to detect, identify, and quantify vapors and vapor mixtures. One implementation of this strategy involves the use of arrays of chemically-sensitive resistors made from conducting polymer composites. Sorption of an analyte into the polymer composite detector leads to swelling of the film material. The swelling is in turn transduced into a change in electrical resistance because the detector films consist of polymers filled with conducting particles such as carbon black. The differential sorption, and thus differential swelling, of an analyte into each polymer composite in the array produces a unique pattern for each different analyte of interest, Pattern recognition algorithms are then used to analyze the multivariate data arising from the responses of such a detector array. Chiral detector films can provide differential detection of the presence of certain chiral organic vapor analytes. Aspects of the spaceflight qualification and deployment of such a detector array, along with its performance for certain analytes of interest in manned life support applications, are reviewed and summarized in this article.
Soft materials that exhibit compliance, programmability, and reconfigurability can have a transformative impact as electronic skin for applications in wearable electronics/soft robotics. There has been significant progress in soft conductive materials; however, achieving electrically controlled and reversible changes in conductivity and circuit connectivity remains challenging. To overcome this limitation, a soft material architecture with reconfigurable conductive networks of silver flakes embedded within a hydrogel matrix is presented. The conductive networks can be reversibly created/disconnected through various stimuli, including current, humidity, or temperature. Such stimuli affect electrical connectivity of the hydrogel by controlling its water content, which can be modulated by evaporation under ambient conditions (passive dehydration), evaporation through electrical Joule heating (active dehydration), or absorption of additional water (rehydration). The resulting change in electrical conductivity is reversible and repeatable, endowing the composite with on-demand reconfigurable conductivity. To highlight this material's unique properties, it is shown that conductive traces can be reconfigured after severe damage and revert to lower conductivity after rehydration. Additionally, a quadruped robot is demonstrated that can respond to stimuli by changing direction following exposure to excess water, thereby achieving reprogrammable locomotion behaviors.
Abstract Li + ‐conducting oxides are considered better ceramic fillers than Li + ‐insulating oxides for improving Li + conductivity in composite polymer electrolytes owing to their ability to conduct Li + through the ceramic oxide as well as across the oxide/polymer interface. Here we use two Li + ‐insulating oxides (fluorite Gd 0.1 Ce 0.9 O 1.95 and perovskite La 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O 2.55 ) with a high concentration of oxygen vacancies to demonstrate two oxide/poly(ethylene oxide) (PEO)‐based polymer composite electrolytes, each with a Li + conductivity above 10 −4 S cm −1 at 30 °C. Li solid‐state NMR results show an increase in Li + ions (>10 %) occupying the more mobile A2 environment in the composite electrolytes. This increase in A2‐site occupancy originates from the strong interaction between the O 2− of Li‐salt anion and the surface oxygen vacancies of each oxide and contributes to the more facile Li + transport. All‐solid‐state Li‐metal cells with these composite electrolytes demonstrate a small interfacial resistance with good cycling performance at 35 °C.
The invention relates to lithium ion batteries and, more particularly, to lithium ion conducting composite polymer electrolyte separators. The separators include a nanofiber mat composed of electrospun nanofibers. The nanofibers include a polymer having one or more polar halogen groups, a lithium-containing solid or liquid electrolyte and nanoparticle filler. The polymer, electrolyte and filler are combined to form a solution that is subjected to the electro-spinning process to produce electrospun nanofibers in the form of the mat.