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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Toward Optimizing Electrospun Nanofiber Fuel Cell Catalyst Layers: Microstructure and Pt Accessibility

This work investigates how local ionomer/platinum (Pt) interactions and ionomer distribution in electrospun Pt/Vulcan nanofiber electrodes impact ionomer coverage, proton accessibility, and oxygen reduction reaction (ORR) performance in proton-exchange membrane fuel cells. Insights from various in situ electrochemical diagnostics were utilized in conjunction with ex situ microscopic characterization to understand how the electrode microstructure—both at the aggregate level and near the ionomer/platinum interface—is affected by electrospinning in comparison to ultrasonic spraying. The effect of the carrier polymer poly(acrylic acid) (PAA) concentration from 5–20 wt % (with respect to total ink solids) on the resulting nanofiber morphology is discussed. Electron microscopy observations and CO displacement measurements indicated that Pt/Vulcan nanofibers prepared with a higher PAA concentration (15 wt %) were conformally coated with a film of ionomer on the exterior of the fiber, which resulted in an overall lower ionomer coverage on both Pt and carbon throughout the fiber diameter. In contrast, 10 wt % PAA leads to a uniform intrafiber distribution of the ionomer within the fibers, increasing the overall ionomer coverage and proton accessibility under both wet and dry conditions. These differences in the local ionomer coverage on Pt between 10 and 15 wt % PAA were also attributed to differences in the adsorption/interaction affinities between PAA and the ionomer onto the catalyst surface in the ink using zeta potential measurements. Additional fuel cell electrochemical tests on the electrospun electrodes show improvements in ORR kinetics and high-current-density H 2 /air performance compared to the ultrasonically sprayed electrodes.

25 ENERGY STORAGE↗
DOE OSTI2020

The Study of the Binder Poly(acrylic acid) and Its Role in Concomitant Solid–Electrolyte Interphase Formation on Si Anodes

In this work we use neutron reflectometry to study how the polymeric binder, poly(acrylic acid) (PAA), affects the in situ formation and chemical composition of the solid–electrolyte interphase (SEI) formation on a silicon anode at various states of charge. The reflectivity is correlated with electrochemical quartz crystal microbalance to better understand the viscoelastic effects of the polymer during cycling. The use of model thin films allows for a well-controlled interface between the amorphous Si surface and the PAA layer. If the PAA perfectly coats the Si surface and standard processing conditions are used, the binder will prevent the lithiation of the anode. The PAA suppresses the growth of a new layer formed at early states of discharge (open circuit voltage to 0.8 V vs Li/Li+), protecting the surface of the anode. At 0.15 V, the SEI layer underneath the PAA changes in chemical composition as indicated by an increase in the scattering length density and thickness as the layer incorporates components from the electrolyte, most likely the salt. At lithiated and delithiated states, the SEI layer changes in chemical composition and grows in thickness with delithiation and shrinks during lithiation.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Effect of Initial Water Saturation on The Performance of Fracturing Fluids With and Without Polyallylamine under Simulated EGS Conditions

Objectives/Scope: StimuFrac (US Patents 9,873,828 B2 and 9,447,315 B2), a CO2-reactive polymer aqueous solution [polyallylamine (PAA) 1wt% in water] combined with CO2, can be used as a less water-intensive fracturing fluid for enhanced geothermal systems (EGS). Our previous results show that in hot dry rock (HDR), PAA/CO2 fracturing fluids outperformed other fluids such as water, CO2, and CO2/water in generating large fractures with less fluid consumed. The objective of this work is to study the effect of initial water saturation of rock on the performance of StimuFrac fluid in ½ foot cubic rock samples and under representative EGS pressure/temperature conditions using cyclic and constant flow rate injection strategies. The fracturing results are compared with results using different fracturing fluids in terms of controlling fracture propagation rates, fracture hydraulic conductivity, breakdown pressures and volumes of fluids required. Methods/Procedures/Process: In all tests, water was initially injected into the rock to increase the water saturation before the fracturing processes to simulate actual geothermal reservoir conditions. For the cyclic injection, one complete cycle consisted of (1) a PAA slug (or water slug) injection followed by (2) CO2 injection to initiate the fracture. In the second step of the first cycle, the pressure of CO2 is increased until a maximum pressure is reached (fracture is initiated at this moment), and then the injection of CO2 is allowed for another 30 seconds to propagate the fracture. Then, the two-step cycle of PAA followed by CO2 injection (up to 2-4 mL/min) was continued. For the constant flow rate injection strategies, the initial water saturation was increased by injecting water at 1000 psi and 200°C for three days. After that, an initial slug of water, CO2, or PAA was injected and then fracturing was initiated and propagated by injecting CO2 at a constant flow rate. Applications/Significance/Novelty: The results of this study suggest that water saturation, especially near the wellbore region, will significantly affect the fracturing fluid transmission into the rock porous media by changing the relative permeability of CO2 or water, thus affecting the fracture initiation and propagation. In this study, fracturing with cyclic injection or constant flow rate injection methods were performed using three different kinds of fluids systems. These fluids are water, CO2, or CO2 with PAA. Splitting the rock samples in half after fracturing reveals that the fracture propagation is significantly limited under these high water saturated conditions compared to dry initial conditions: The fractures propagate less than 1/3 length of the distance from the wellbore to rock surface, and in some cases no fracture is generated. This may be caused by the fact that leak-off is dominating the fracturing process and the injected fluid flow rate is not high enough to overcome the leak-off even under high flow rate injection conditions. Additionally, CO2 could be leaking off into the wellbore annulus and this may be making it more difficult to generate pressure gradients away from the near-wellbore region.

Jian, Guoqing↗
DOE OSTI2023

Effect of initial water saturation on the performance of fracturing fluids with and without polyallylamine under simulated EGS conditions

Objectives/Scope: StimuFrac (US Patents 9,873,828 B2 and 9,447,315 B2), a CO 2 - reactive polymer aqueous solution [polyallylamine (PAA) 1wt% in water] combined with CO 2 , can be used as a potentially less water-intensive fracturing fluid for enhanced geothermal systems (EGS). Our previous results show that in hot dry rock (HDR), PAA/CO 2 fracturing fluids outperformed other fluids such as water, CO 2 , and CO 2 /water in generating large fractures with less fluid consumed. The objective of this work is to investigate the effect of initial water saturation on the performance of StimuFrac by conducting hydraulic fracturing tests with ½ foot cubic rock samples held under representative EGS stress/temperature conditions and by using cyclic injection strategies (under constant injection rate). The resulting fracture hydraulic conductivities, breakdown pressures, and volumes of fluids required are compared. Methods/Procedures/Process: To simulate geothermal reservoir conditions, in all tests, the rock sample was held under triaxial confinement and at 200 °C, and different volumes of water were initially injected into the rock sample before any fracturing processes were initiated. For the single-cycle PAA (or water) alternating CO 2 (PAG or WAG) injection fracturing experiments, one complete cycle consisted of two steps: (1) injecting a PAA slug (or water slug) followed by (2) injecting CO 2 to initiate and propagate the fracture. For experiments involving multiple injection cycles, the CO 2 injection pressure is increased until it peaks and begins to decline (indicating fracture initiation at this moment), and then continued being injected for another 30 seconds to propagate the fracture. Then, these two-step cycles [injection of PAA (or water) followed by CO 2 injection (up to 2-4 mL/min)] are repeated. Applications/Significance/Novelty: The results of this study suggest that water saturation significantly affects the fracturing fluid transmission into the rock pore space, thus affecting the fracture initiation and propagation. In this study, fracturing tests via a single injection cycle or multiple injection cycles were performed. Splitting the rock samples in half after testing reveals that fracture propagation is significantly limited under high water saturation conditions (three-day initial water injection) compared to stimulation experiments performed in hot dry rock. The fractures propagate less than 1/3 of the distance from the wellbore to the outer rock surface, and in some cases, no fracture is generated. This may be caused by leak-off dominating the fracturing process and the fluid injection rate is insufficient to overcome leak-off, even under high injection rate conditions. Additionally, CO 2 could be leaking off into the wellbore annulus and this may be making it more difficult to generate sufficiently high-pressure gradients away from the near-wellbore region. Under low water saturation conditions (dry rock or after 1-day initial water injection), PAA/CO 2 consistently generated significantly larger fractures compared with the other fluids. CO 2 generated large fractures only in the hot dry rock and only when using high injection rates, though data variability is high.

58 GEOSCIENCES↗
DOE OSTI2021

Role of Low Molecular Weight Polymers on the Dynamics of Silicon Anodes During Casting

This work probes the slurry architecture of a high silicon content electrode slurry with and without low molecular weight polymeric dispersants as a function of shear rate to mimic electrode casting conditions for poly(acrylic acid) (PAA) and lithium neutralized poly(acrylic acid) (LiPAA) based electrodes. Rheology coupled ultra-small angle neutron scattering (rheo-USANS) was used to examine the aggregation and agglomeration behavior of each slurry as well as the overall shape of the aggregates. The addition of dispersant has opposing effects on slurries made with PAA or LiPAA binder. With a dispersant, there are fewer aggregates and agglomerates in the PAA based silicon slurries, while LiPAA based silicon slurries become orders of magnitude more aggregated and agglomerated at all shear rates. The reorganization of the PAA and LiPAA binder in the presence of dispersant leads to a more homogeneous slurry and a more heterogeneous slurry, respectively. This reorganization ripples through to the cast electrode architecture and is reflected in the electrochemical cycling of these electrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Synergistically combining peracetic acid and reduced graphene oxide membranes to degrade trace organic contaminants

The removal of trace organic contaminants is a critical step for the reuse of municipal and industrial wastewater. Herein, we demonstrate a catalytic membrane platform synergistically integrating reduced graphene oxide (rGO) membranes and peracetic acid (PAA) oxidation, using a dye of methylene blue (MB) and a pesticide of 2,4-dichlorophenoxyacetic acid (2,4-D) as model contaminants. In a crossflow system with rGO membrane and 25 ppm PAA, the degradation rates of MB and 2,4-D were 22 and 0.12 g h −1 per g rGO, with an initial concentration of 10 and 1.1 ppm, respectively. The degradation time profile of MB and 2,4-D follows a pseudo-first-order model, and the degradation rate constant increases with increasing initial PAA doses. Here, the rGO membranes also exhibited good stability over a 1-month test for 2,4-D degradation. In addition to the nanofiltration performance of the rGO membrane, the integrated PAA-rGO membrane process shows great potential to degrade various organic contaminants without the need to separate and recover the metal-free catalyst in downstream treatment.

2,4-D↗
DOE OSTI2025

Composite biopolymer electrolytes for high-performance reversible zinc-air batteries

Zinc-air batteries (ZABs) are regarded as one of the most promising candidates for next-generation energy storage systems due to their inherent safety, high energy density, and low cost. In this study, we optimized the composition of gel polymer electrolytes (GPEs), which play a crucial role in enhancing ZAB reversibility due to their water retention capabilities. The GPEs are synthesized using a combination of polyacrylic acid (PAA), polyacrylamide (PAM), and biopolymer kappa-carrageenan (KC), with and without additional additives. Among these, the composite GPE containing KC, PAA, and PAM demonstrated superior ionic conductivity (6.68 mS/cm at 30 °C) and enhanced water retention compared to the PAA–PAM-based GPE. Furthermore, this composite electrolyte operates within a wider electrochemical window of −1.0 V–2.2 V. A bifunctional catalyst, nickel–iron layered double hydroxide (NiFe-LDH), is electrochemically synthesized on a modified activated carbon cloth (CC). The catalyst loading is optimized based on oxygen evolution reaction (OER) performance, showing an overpotential of 555 mV. The oxygen reduction reaction (ORR) occurred at a half-wave potential of 0.620 V, which is lower than that of Pt/C (0.852 V), indicating better catalytic activity. The KC based cell exhibit better cycling stability than PAA–PAM-based GPE. The electrochemical performance of ZAB cells is evaluated under various atmospheres: ambient air and humid conditions and temperatures. Notably, in a humid environment, the cells achieved extended cycling stability, operating for over 500 h—significantly longer than under open-air conditions. Overall, this study highlights the importance of tailored GPE design and efficient bifunctional catalysts to enhance the performance and longevity of zinc-air batteries for long-duration energy storage applications.

Catalyst↗
DOE OSTI2022

Specific Ion and Electric Field Controlled Diverse Ion Distribution and Electroosmotic Transport in a Polyelectrolyte Brush Grafted Nanochannel

Controlling ion distribution inside a charged nanochannel is central to using such channels in diverse applications. Here, we show the possibility of using a charged polyelectrolyte (PE) brush grafted nanochannel for triggering diverse nanoscopic ion distribution and nanofluidic electroosmotic transport by controlling the valence and size of the counterions (that screen the charges of the PE brushes) and the strength of an externally applied axial electric field. We atomistically simulate separate cases of fully charged Polyacrylic acid (PAA) brush functionalized nanochannels with Na + , Cs + , Ca 2+ , Ba 2+ , and Y 3+ counterions screening the PE charges. Four key findings emerge from our simulations. First, we find that the counterions with a greater valence and a smaller size prefer to remain localized inside the brush layer. Second, for the case where there is an added chloride salt with the same cation (as the screening counterions), there are more coions (Cl - ions) in the brush-free bulk than counterions (for counterions Na + , Ca 2+ , Ba 2+ , Y 3+ ): this is a manifestation of the overscreening (OS) of the PE brush layer. Contrastingly, the number of Cs + ions remain higher than the Cl - ions inside the brush-free bulk, ensuring that there is no OS effect for this case. Third, large applied electric field enables a few Na + , Cs + , and Ba 2+ counterions to leave the brush layer and to go to the bulk: this makes the OS of the PE brush layer disappear for the cases of PE brushes being screened by the Na+ and Ba 2+ ions. On the other hand, no such electric-field-mediated disappearance of OS is observed for the cases of Ca 2+ and Y 3+ screening counterions; we attribute this to the firm attachment of these counterions to the negatively charged monomers. Free energy associated to a counterion binding to a PE chain corroborates this diversity in the counterion-specific response to the applied electric field. Lastly, we demonstrate that such diverse ion distributions, along with specific electric-field-strength-dependent ion properties, lead to (1) EOS transport in nanochannels grafted with PAA brushes screened with Cs + ions to be always counterion dominated, (2) EOS transport in nanochannels grafted with PAA brushes screened with Ca 2+ and Y 3+ ions to be always coion dominated, and (3) EOS transport in nanochannels grafted with PAA brushes screened with Na + and Ba 2+ ions to be coion dominated for smaller electric fields and counterion dominated for larger electric fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Plasma-Initiated Graft Polymerization of Acrylic Acid onto Fluorine-Doped Tin Oxide as a Platform for Immobilization of Water-Oxidation Catalysts

The discovery of new and versatile strategies for the immobilization of molecular water-oxidation catalysts (WOCs) is crucial for developing clean energy conversion devices [e.g., (photo)electrocatalytic cells for water splitting]. The traditional approach for surface attachment to transparent conductive oxides [e.g., fluorine doped tin oxide (FTO)] is via synthetic modification of the ligand architecture to incorporate functional groups such as carboxylic acids (-COOH) or phosphonates (-PO 3 H 2 ) prior to immobilization. However, challenges arising from desorption and the cumbersome derivatizations steps have limited the scope and applications of surface-bound WOCs. Herein, we report the successful immobilization of underivatized Ru(II)-based WOCs (Ru–Cat1 = [Ru(tpy) (bpy) (H 2 O)] 2+ (tpy = 2,2':6'2"–terpyridine and bpy = 2,2;-bipyridine) and Ru–Cat2 = [Ru(Mebimpy) (bpy) (H 2 O)] 2+ (Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl) pyridine)) and the Ru(II) polypyridyl chromophore Ru–C3 = [Ru(bpy) 3 ] 2+ onto a FTO plasma-grafted poly(acrylic acid) surface (PAA|FTO). Various characterization techniques such as attenuated total reflectance Fourier transform infrared spectroscopy, scanning electron microscopy, atomic force microscopy, and cyclic voltammetry measurements provide evidence for the plasma-induced grafted PAA|FTO film and immobilization. Surface stability and electrocatalytic properties of these new hybrid composite films upon cycling were investigated at different pH values. Immobilized Ru–Cat1 and Ru–Cat2 onto PAA|FTO displayed pH-dependent (RuIII/RuII) couples and onset potentials indicative of PCET (proton-coupled electron transfer) reactions. Based on cyclic voltammetry results and spectroscopic monitoring, the immobilized WOCs Ru–Cat1 and Ru–Cat2 exhibited a higher surface stability in neutral aqueous solutions relative to Ru–C3 upon electrochemical oxidation. Furthermore, we attribute the surface PCET and stability to the presence of a water ligand in the coordination sphere of immobilized Ru–Cat1 and Ru–Cat2 which can H-bond with negatively charged carboxylate groups of the cross-linked PAA brushes. Our findings demonstrate that the plasma-grafted polymeric network onto FTO offers a versatile platform to directly anchor unmodified homogeneous WOCs or chromophores for potential applications in solar-to-fuel energy conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Molecular dynamics study on the interfacial properties of mixtures of monomers of polyvinylpyrrolidone (PVP)-based battery binders on graphene and graphite surfaces

This study investigates the behavior of two different mixtures of monomers of polyvinylpyrrolidone (PVP)-based battery binders, polyvinylpyrrolidone:polyvinylidene difluoride (PVP:PVDF) and polyvinylpyrrolidone:polyacrylic acid (PVP:PAA), at graphene and graphite interfaces using classical molecular dynamics simulations. The aim is to identify the best performing monomer binder blend and carbon-based material for the design of battery-optimized energy devices. The PVP:PAA monomer binder blend and graphite are found to have the best interaction energies, densification upon adsorption, and more ordered structure. The adsorption of both monomer binder blends is strongly guided by the higher affinity of PVP and PAA monomeric molecules for the surfaces compared to PVDF. The structure of adsorbed layers of PVP:PVDF monomer binder blend on graphene and graphite develops more quickly than PVP:PAA, indicating faster kinetics. This study complements a previous density functional theory study recently reported by our group and contributes to a better understanding of the nanoscopic features of relevant interfacial regions involving mixtures of monomers of PVP-based battery binders and different carbon-based materials. In conclusion, the effect of a blend of commonly used monomer binders on carbon-based materials is essential for obtaining tightly bound anode and cathode active materials in lithium-ion batteries, which is crucial for designing battery-optimized energy devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Anti-Icing Coatings using Ionomer Film Layer Structuring

This research effort examined the application of Nafion polymers in alcohol solvents as an anti-ice surface coating, as a mixture with hydrophilic polymers and freezing point depressant salt systems. Co-soluble systems of Nafion, polymer and salt were applied using dip coating methods to create smooth films for frost observation over a Peltier plate thermal system in ambient laboratory conditions. Cryo-DSC was applied to examine freezing events of the Nafion-surfactant mixtures, but the sensitivity of the measurement was insufficient to determine frost behavior. Collaborations with the Fog Chamber at Sandia-Albuquerque, and in environmental SAXS measurements with CINT-LANL were requested but were not able to be performed under the research duration. Since experimental characterization of these factors is difficult to achieve directly, computational modeling was used to guide the scientific basis for property improvement. Computational modeling was performed to improve understanding of the dynamic association between ionomer side groups and added molecules and deicing salts. The polyacrylic acid in water system was identified at the start of the project as a relevant system for exploring the effect of varying counterions on the properties of fully deprotonated polyacrylic acid (PAA) in the presence of water. Simulations were modeled with four different counterions, two monovalent counterions (K+ and Na+) and two divalent counterions (Ca2+ and Mg2+). The wt% of PAA in these systems was varied from ~10 to 80 wt% PAA for temperatures from 250K to 400K. In the second set of simulations, the interpenetration of water into a dry PAA film was studied for Na+ or Ca2+ counterions for temperatures between 300K and 400K. The result of this project is a sprayable Nafion film composite which resists ice nucleation at -20 °C for periods of greater than three hours. It is composed of Nafion polymer, hydrophilic polyethylene oxide polymer and CaCl2 anti-ice crosslinker. Durability and field performance properties remain to be determined.

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

Fuel Cell Membrane Electrode Assemblies with Ultra-Low Pt Nanofiber Electrodes (Final Report)

H 2 /air fuel cell membrane-electrode-assemblies (MEAs) were fabricated with electrospun particle/polymer nanofiber mat cathodes (0.1 mg Pt /cm 2 or 0.2 mg Pt /cm 2 Pt/C, PtCo/C or PtNi/C) and anodes (0.1 mg/cm 2 Pt/C), where the binder was a mixture of acid-form perfluorosulfonic acid ionomer (e.g., Nafion™) and poly(acrylic acid) (PAA) carrier polymer or sodium-form PFSA with a carrier polymer of either PAA or polyethylene oxide (PEO). For the latter two cases, the water-soluble carrier was removed from the fibers after electrospinning. MEAs with Pt/C anode/cathode catalyst loadings of 0.1 mg Pt /cm2 each, an 1100 EW PFSA binder (Nafion™ dispersion), and a Nafion 211 membrane produced high power at both high and low relative humidity (RH) conditions, e.g., a maximum power density of 919 mW/cm 2 at 100% RH and 832 mW/cm 2 at 40% RH for a test at 80 °C and 200 kPa abs . The high power at low RH was attributed to nm-size pores within the fibers that trap water via capillary condensation thus maintaining a high proton conductivity of the PFSA binder in the cathode and especially the anode while minimizing/eliminating ionic isolation of catalyst particles in low water content, poorly conductive binder. At the same time, micro-porosity between fibers in the cathode allows for fast removal of electrogenerated water, thus minimizing cathode flooding. Nanofiber MEAs with Pt alloy catalyst cathodes also performed well, where a fibrous PtCo/C catalyst cathode at a loading of 0.1 mg/cm 2 produced 20% more power than a conventional powder cathode MEA, e.g., a maximum power density of 1,045 mW/cm 2 vs. 869 mW/cm 2 at 80 °C, 100% RH, and 200 kPa abs , and a PtNi/C fiber cathode MEAs prepared with Na+-form Nafion + PEO generated a maximum power of 820 mW/cm 2 at 40% RH. Fiber electrode MEAs with a neat Nafion binder (prepared from Na+-form Nafion + PEO or PAA) where the cathode Pt loading was ~0.1 mg/cm 2 exhibited a 25% loss in maximum power at 30,000 metal dissolution cycles, as compared to a 12% loss when the cathode binder was H+-form Nafion + PAA. The performance of a fiber mat electrode MEA with Pt/C catalyst (0.2 mg/cm 2 cathode loading and 0.1 mg/cm 2 anode loading) was excellent. At 80 oC and 200 kPa abs , the maximum power density was 1104 mW/cm 2 . The maximum power was independent of feed gas humidity for 40 < RH < 100%. The power loss after a metal dissolution AST (30,000 voltage cycles) was only 13%.

08 HYDROGEN↗
DOE OSTI2020

Foot-scale Evaluation of CO2-Responsive Polymer and CO2 Binary Fluid as an Alternative Fracturing Fluid for Enhanced Geothermal Systems

A foot-scale high-temperature true-triaxial fracturing apparatus was used to conduct hydraulic fracture tests on rock samples. The fracturing tests used different fluids including water, CO2, CO2 with water, and CO2 with a 1% polyallylamine (PAA)/water solution. The tests were conducted with both constant pressure injection and constant flow rate injection modes. CO2-based fracturing fluids were found to produce higher breakdown pressures, high transient flow rates, and produce higher-conductivity fractures as compared to water-based fracturing fluids. Additionally, faster pressurization rates with CO2-based fracturing fluids (obtained when fracturing at constant flow rate mode) are found to be associated with higher fracture conductivities. When fracturing with CO2-based fluids in the presence of a PAA aqueous solution, for example if the rock is saturated with 1wt% PAA in water, the volume expansion caused by CO2-induced crosslinking of PAA leads to a faster pressure increase due to the associated volume expansion and increase in viscosity. It was also found that CO2 as a fracturing fluid injected in hot dry rock (HDR) attain the highest fracture conductivity only when injected at very high flow rates, followed very closely by the CO2/PAA fracturing fluid system that generates fractures with, on average, similarly high conductivity values though independently of injection flow rate and using 1/6 of the mass of CO2 as compared to CO2 in HDR. Breakdown pressures were also similar for CO2 stimulation in HDR and CO2/PAA fluid system under identical injection flow rates. Finally, the well-known low viscosity of CO2 phase prevents the efficient transport of proppants while the reacted CO2/PAA fluid system is known to form a high viscosity binary fracturing fluid system with the potential to carry proppant in addition of being a fine fracturing fluid.

Enhanced Geothermal Systems, polyallylamine, Co2-r↗
DOE OSTI2020

Alternative, Less Water-Intensive, Fracturing Fluids for Enhanced Geothermal Systems

Four fracturing fluids; water, CO2, CO2 with water, and CO2 with an aqueous solution of a CO2-reactive polymer, poly(allylamine) (PAA, 1wt%) were evaluated using a high-temperature true-triaxial fracturing apparatus and ½ foot side granite cubic samples. All three CO2-based fracturing fluids, CO2, CO2 with water, and CO2 with aqueous PAA fractured granite at higher breakdown pressures, high transient flow rates, and produce higher-conductivity fractures as compared to water. Additionally, faster pressurization rates with CO2-based fracturing fluids (obtained when fracturing at constant flow rate mode) are found to be associated with higher fracture conductivities. When partially saturating the rock sample with PAA solution followed by fracturing with CO2, the volume expansion caused by CO2-induced cross-linking of PAA leads to a faster pressure increase due to the associated stress generated and increase in viscosity. It was also found that CO2 as a fracturing fluid injected in hot dry rock (HDR) attain the highest fracture conductivity only when injected at very high flow rates, followed very closely by the CO2/PAA fracturing fluid system that generates fractures with, on average, similarly high conductivity values though independently of injection flow rate and using 1/6 of the mass of CO2 as compared to CO2 in HDR. Breakdown pressures were also similar for CO2 stimulation in HDR and CO2/PAA fluid system under identical injection flow rates. It is concluded that CO2 (when injected in HDR) and CO2/PAA are the fluids of choice for stimulation of granitic rock samples under the studied geothermal P/T conditions. CO2/PAA, however, offer the following three additional advantages; 1) it requires significantly lower volumes of CO2, 2) fracture permeability is independent of injection flow rate, and 3) the reversible (previously reported) viscosity increase is beneficial to transport proppants if they are ever developed enhanced geothermal systems.

Jian, Guoqing↗
DOE OSTI2023

Effect of isopropanol cosolvent on the rheology and spinnability of aqueous polyacrylic acid solutions

Abstract We investigate the effect of alcohol fraction (isopropanol, IPA) in a binary water‐alcohol solvent mixture on the shear and extensional rheological properties, as well as the role of viscoelasticity on fiber formation of poly(acrylic acid) (PAA) in electrospinning. Comparison of the scaling of both specific viscosities η sp and extensional relaxation times λ E of PAA in water–IPA mixtures, showed stronger scaling compared to salt‐free aqueous polyelectrolyte solutions, except for the η sp in the unentangled regime displaying a polyelectrolyte‐like scaling η sp ~ c 0.5 for all IPA%. Such deviation suggested IPA induces association/aggregation of PAA. However, the trends between η sp and λ E magnitudes as a function of IPA% differ for concentrations compared in the entangled regime. The η sp as well as their elastic moduli exhibit a maximum, whereas λ E increases monotonically with IPA%, suggesting a complex interplay of various interactions are dictating their structure in water‐IPA mixtures, affecting their shear and extensional response differently. Electrospinning experiments showed increasing IPA% reduces the onset of both beaded and uniform fibers. Analysis using dimensionless numbers indicated the enhancement of their elasticity by IPA, and the consequent stabilizing effect on their jets/filaments against break‐up during electrospinning, plays a role in the improvement of their fiber formation.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Enabling aqueous processing for LiNi 0.80 Co 0.15 Al 0.05 O 2 (NCA)-based lithium-ion battery cathodes using polyacrylic acid

Replacing N-methyl-2-pyrrolidone (NMP) with water in the production of lithium-ion battery cathodes is critical to realizing process cost savings and improved worker safety. LiNi 0.80 Co 0.15 Al 0.05 O 2 (NCA) is a poor fit for aqueous processing due to destructive Al current collector corrosion resulting from highly basic slurries and detrimental surface reconstruction reactions that occur in water. In this study, polyacrylic acid (PAA, MW = 450,000 g·mol -1 ) is examined as a corrosion-mitigating and surface-stabilizing agent. Adding PAA to an aqueous NCA slurry can provide a stable pH (4.0–8.5) for at least 4 h, since the carboxyl groups from PAA dissociate and increase the proton concentration in the slurry. Further, these groups can also adsorb to the surface of NCA particles and provide electrostatic stability from active material particle agglomeration, as revealed by zeta potential measurements. Minor cracking does occur at the electrode surface; this cracking likely caused poorer adhesion to the Al current collector in the aqueous-processed film when compared to the NMP-processed baseline. Electrochemically, the leached Li does cause a lower initial capacity for the aqueous-processed cathode, though the capacity retention of the aqueous-processed cathode is better than the baseline. The cracks in the coating led to a rise in charge transfer resistance that hindered rate capability above 1C.

25 ENERGY STORAGE↗
DOE OSTI2024

Stabilizing a low temperature phase change material based on Glaubers salt

The aim of this research is to enhance the performance of Glauber's salt (sodium sulfate decahydrate, SSD) as a phase change material (PCM) for thermal energy storage applications, as well as for shipping of temperature-sensitive materials. The study investigates the effects of modifying SSD with potassium chloride (KCl) and ammonium chloride (NH 4 Cl) to achieve lower phase transition temperatures of between +6 °C and + 13 °C. Sodium polyacrylate (PAAS) is employed as a thickening agent to prevent phase separation, and borax is used as a nucleating agent to suppress supercooling. Various ratios of KCl:NH 4 Cl are tested, and the impact of PAAS concentration on phase segregation is explored. The results show that a 2 wt% concentration of PAAS effectively prevents phase separation. Samples with a KCl:NH 4 Cl ratio of 1:1.83 exhibit stable phase transition behavior and maintain latent heat values within the range of 130–140 J/g after 30 thermal cycles. Maintaining a total KCl and NH 4 Cl proportion of 10 wt% is crucial to achieve the desired lower melting temperature. As a result, the study highlights the significance of thermal cycling in improving the stability of the PCM. The optimized SSD-based eutectic PCM formulations hold promise for applications in the cold chain industry.

25 ENERGY STORAGE↗