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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 595 records · Page 33

Performance and Durability of Hybrid Fuel Cell Systems for Class-8 Long Haul Trucks

Hybrid fuel cell-battery configurations are investigated that overcome thermal management issues in fuel cell powertrains for heavy-duty Class 8 trucks. The battery is sized so that it has sufficient capacity to provide supplemental power and energy on a hill climb transient at end-of-life. A dynamic load sharing strategy is developed to distribute the power demand between the fuel cell system (FCS) and the energy storage system in a manner that optimizes their lifetimes. The FCS end-of-life is identified as the terminal point beyond which the stack cannot generate the rated power with target power density at 0.7 V and 40 °C ambient temperature. Reaching the target lifetime with a-Pt/C cathode catalyst in one hybrid configuration requires voltage clipping to 813 mV, idle power limited to 50 kW, catalyst overloading to 0.45 mg cm -2 total Pt in anode and cathode, and 44% active membrane area oversizing. The stack and FCS drive cycle efficiencies decrease by 4.2% and 5.4%, respectively, during the electrode lifetime. Further, the FCS performance, durability and cost are compared with the targets of 68% peak efficiency, 0.30 mg cm -2 total Pt loading, 2.5 kW/g PGM Pt group metal (PGM) loading, 750 mW cm -2 power density, 25,000-h lifetime and $80/kW cost.

33 ADVANCED PROPULSION SYSTEMS↗

Mitigating Crack Formation When Using High Oxygen Permeability Ionomer in PEMFC Catalyst Layers

High oxygen permeability ionomers (HOPIs) are being developed as an alternative to conventional perfluorosulfonic (PFSA) ionomers for cathodes in proton exchange membrane fuel cells (PEMFCs). HOPIs aim to reduce local oxygen transport resistance, improving performance and reducing degradation as the catalyst loses surface area. However, HOPIs' more rigid, 3D backbone leads to increased crack density in the cathode, potentially causing accelerated degradation. This study investigates crack formation in HOPI-based and PFSA-bound catalyst layers (CLs). We conducted a comprehensive parametric study to identify conditions and catalyst slurry components that minimize cracking. CLs were fabricated with various ionomer and catalyst types, under different relative humidity (RH) levels, solids weight percentages, solvent ratios, and ionomer-to-carbon ratios (I/C). Results show that HOPI-based CLs exhibit less cracking when fabricated under low RH conditions, with lower solids weight percentage, higher alcohol content, and lower I/C. Additionally, catalysts with low/medium surface area carbon supports show less cracking than those with high surface area carbon supports.

08 HYDROGEN↗

Membrane Pretreatment and Cell Conditioning for Proton Exchange Membrane Water Electrolysis

As the research community studying proton exchange membrane water electrolysis (PEMWE) grows, it is important to develop methods that achieve transparent, reproducible research. Reproducibility of performance and durability is a challenge facing the PEMWE field, as the published literature includes a wide spread of results obtained with nominally similar materials. Prior round-robin performance benchmarking efforts [1] have identified inadequate cell conditioning as a major source of variation in apparent cell performance. Inadequate pre-treatment and conditioning can lead to instability in initial performance and adds ambiguity to durability measurements. However, excessively prolonged conditioning procedures limit the throughput of testing and the pace of research. Pretreatment and conditioning methods vary significantly across the research literature, but little systematic investigation is available into the mechanisms of these procedures or how procedural differences may impact results. This presentation will discuss investigations into the effects of membrane pre-treatment and operating procedures during cell conditioning on initial performance and catalyst-specific accelerated stress tests, with the aim of recommending procedures to enable clear, reproducible, and high-throughput research. Methods investigated include the use of hydrogen peroxide, acids, and hydration at elevated temperature for membrane pretreatment, and conditioning procedures such as current or voltage holds and cycling. The investigations cover both the impacts of these procedures on cell performance and stability as well as underlying mechanisms and processes taking place in the cell materials.

cell↗

Batteries 2022 Annual Progress Report

This document summarizes the progress of VTO battery R&D projects supported during the fiscal year 2022. Its R&D focus was on the development of high-energy batteries for PEVs. The electrochemical energy storage roadmap describes ongoing and planned efforts to develop electrochemical storage technologies for EVs. To advance battery technology, which can in turn improve market penetration of PEVs, the program investigates various battery chemistries to overcome specific technical barriers, e.g., battery cost, performance, life (both the calendar life and the cycle life), its tolerance to abusive conditions, and its recyclability/sustainability.

25 ENERGY STORAGE↗

Production of Renewable Natural Gas from Waste Carbon Dioxide Sources (CRADA Final Report)

This CRADA provides new funding from SoCalGas and DOE's BETO and FCTO Offices focused hydrogen mass transfer limitations in H2@Scale processes. The project leverages the existing hydrogen production capabilities at the Energy Systems Integration Facility (ESIF) and SoCalGas' 700 L bioreactor system designed, built, and delivered to NLR under the first phase of this CRADA. This Joint Work Statement will cover new hardware modifications between NLR's electorlyzer stack and the SoCalGas bioreactor located outdoors. The new hardware and controls will provide researchers with the tools needed to obtain preliminary experimental data for a non-provisional application due in July 2019. The IP being developed is expected to improve the productivity of the bioreactor and would have wider impacts on other end-use processes using pressurized hydrogen (H2). In addition, this new funding enhances an existing BETO Biopower award by developing a 10-15 kW electrolyzer that is scalable to the MW-class with reduced capital cost and higher efficiency aimed at improving H2 mass transfer to downstream processes, like biomethanation. Finally due to the close-coupling between the electrolyzer stack and bioreactor, R&D will focus on cell retention, nutrient maintenance, optimal water management and process controls.

08 HYDROGEN↗

Broadband NMR relaxometry of electrolytes for energy storage

An increasing use of the fast field cycling nuclear magnetic resonance relaxometry technique to investigate dynamics in electrolytes for energy storage has been evidenced during the last decade. Therefore, this review article describes some of the research carried out on electrolytes during the last ten years using this technique. These studies include various types of liquid electrolytes, such as ionic liquids and deep eutectic solvents, semi-solid-state electrolytes, in particular ionogels and polymer gels, and solid electrolytes such as glasses, glass ceramics and polymers. Here, an extended description of the different models used to explain the relaxation rate profiles is presented throughout this article.

25 ENERGY STORAGE↗

Task-Specific Phosphonium Iongels by Fast UV-Photopolymerization for Solid-State Sodium Metal Batteries

Sodium metal batteries are an emerging technology that shows promise in terms of materials availability with respect to lithium batteries. Solid electrolytes are needed to tackle the safety issues related to sodium metal. In this work, a simple method to prepare a mechanically robust and efficient soft solid electrolyte for sodium batteries is demonstrated. A task-specific iongel electrolyte was prepared by combining in a simple process the excellent performance of sodium metal electrodes of an ionic liquid electrolyte and the mechanical properties of polymers. The iongel was synthesized by fast (<1 min) UV photopolymerization of poly(ethylene glycol) diacrylate (PEGDA) in the presence of a saturated 42%mol solution of sodium bis(fluorosulfonyl)imide (NaFSI) in trimethyl iso-butyl phosphonium bis(fluorosulfonyl)imide (P111i4FSI). The resulting soft solid electrolytes showed high ionic conductivity at room temperature (≥10 -3 S cm -1 ) and tunable storage modulus (10 4 –10 7 Pa). Iongel with the best ionic conductivity and good mechanical properties (Iongel10) showed excellent battery performance: Na/iongel/NaFePO 4 full cells delivered a high specific capacity of 140 mAh g -1 at 0.1 C and 120 mAh g -1 at 1 C with good capacity retention after 30 cycles.

25 ENERGY STORAGE↗

Increasing Ionic Conductivity of Poly(ethylene oxide) by Reaction with Metallic Li

Poly(ethylene oxide) (PEO) was the first lithium-ion conducting polymer developed 50 years ago and is still the most popular electrolyte matrix for solid-state lithium metal batteries. While many studies focus on increasing PEO ionic conductivity through doping with Li salts, little work has addressed using PEO and Li directly to generate Li + -conducting species in situ. Reaction between PEO and Li leads to ionic conductivity largely from Li + , in contrast to the case of added salts where the anion contribution dominates. Herein, electrochemical impedance spectroscopy shows the ionic conductivity of PEO thin films increases up to three orders of magnitude (from 10 –7 to 10 –4 S cm –1 ) when contacted with Li at elevated temperature. This is due to the reduction of ether bonds, which produces lithium alkoxides that are responsible for Li + transport. Density functional theory analysis confirms this mechanism as thermodynamically favorable. X-ray photoelectron spectroscopy also shows the presence of organolithium species and Li 2 O, which are responsible for propagating reactions with PEO and forming an electronically insulating layer at the PEO–Li interface that halts further reaction, respectively. The underlying mechanisms of Li–polymer electrolyte reactions is clarified and new pathways for in situ Li + doping of polymer electrolytes is presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unraveling Morphology and Chemistry Dynamics in Fluoroethylene Carbonate Generated Silicon Anode Solid Electrolyte Interphase Across Delithiated and Lithiated States: Relative Cycling Stability Enabled by an Elastomeric Polymer Matrix

The silicon solid electrolyte interphase (SEI) faces cyclical cracking and reconstruction due to the ∼350% volume expansion. Understanding the SEI dynamic morphology and chemistry evolution from delithiated to lithiated states is thereby paramount to engineering a stable Si anode. Fluoroethylene carbonate (FEC) is a preferred additive with widely demonstrated enhancement of the Si cycling. Thus, insights into the dynamics of the FEC-SEI may provide hints toward engineering the Si interface. Herein, complementary ATR-FTIR, AFM, tip IR, and XPS probing reveal the presence of an elastomeric polycarbonate-like matrix in the FEC-generated SEI which is absent from the FEC-free SEI. Adding FEC to the baseline 1 M LiPF 6 in EC:EMC (1:1) electrolyte promotes formation of a thinner and more conformal SEI, and subdues morphology and chemistry changes between consecutive half-cycles. From AFM, morphological stabilization of the FEC-SEI occurs earlier. Furthermore, conventional SEI biproducts such as Li 2 CO 3 and LiEDC appear in reduced quantities in the FEC-SEI implying a reduced quantity of Li-consuming species. The thin polymeric FEC-SEI enables deeper (de)lithiation of silicon. In conclusion, the enhanced mechanical compliance, chemical invariance, and reduced Li inventory consumption of the FEC-SEI are logically the key features underlying the Si cycling enhancement by FEC.

25 ENERGY STORAGE↗

Metal sensitized color changing material

The subject invention pertains to color changeable, film materials comprising a metal substrate layer; a conducting polymer or conducting polymer composite layer; and an electrolyte layer. The conducting polymer or conducting polymer composite layer of the film material is capable of exhibiting changes in one or more optical properties when the film material is in contact with a metal. The subject invention also pertains to methods of preparing conducting polymer films capable of exhibiting changes in optical properties.

Ram, Manoj Kumar↗

Nuclear Magnetic Resonance Relaxation Pathways in Electrolytes for Energy Storage

Nuclear Magnetic Resonance (NMR) spin relaxation times have been an instrumental tool in deciphering the local environment of ionic species, the various interactions they engender and the effect of these interactions on their dynamics in conducting media. Of particular importance has been their application in studying the wide range of electrolytes for energy storage, on which this review is based. Here we highlight some of the research carried out on electrolytes in recent years using NMR relaxometry techniques. Specifically, we highlight studies on liquid electrolytes, such as ionic liquids and organic solvents; on semi-solid-state electrolytes, such as ionogels and polymer gels; and on solid electrolytes such as glasses, glass ceramics and polymers. Although this review focuses on a small selection of materials, we believe they demonstrate the breadth of application and the invaluable nature of NMR relaxometry.

25 ENERGY STORAGE↗

Electrolyte–Electrocatalyst Interfacial Effects of Polymeric Materials for Tandem CO 2 Capture and Conversion Elucidated Using In Situ Electrochemical AFM

Integrating CO 2 capture and electrochemical conversion has been proposed as a strategy to reduce the net energy required for CO 2 regeneration in traditional CO 2 capture and conversion schemes and can be coupled with carbon-free renewable electricity. Polyethylenimine (PEI)-based materials have been previously studied as CO 2 capture materials and can be integrated in these reactive capture processes. PEI-based electrolytes have been found to significantly increase the CO 2 loading, and impact selectivity and rate of product formation when compared to the conventional aqueous electrolytes. However, the influence of these materials at the catalyst–electrode interface is currently not well understood. In this study, PEI-based electrolytes were prepared and their impact on the morphology of a silver electrode performing electrochemical CO 2 reduction (CO 2 R) was studied using in situ electrochemical atomic force microscopy (EC-AFM). The presence of PEI on the electrode surface could be distinguished based on nanomechanical properties (DMT modulus), and changes were observed as negative polarization was applied, revealing a reorganization of the PEI chains due to electrostatic interactions. These changes were impacted by the electrolyte composition, including the addition of supporting electrolyte KHCO 3 salt, as well as CO 2 captured by the PEI-based electrolyte, which minimized the change in surface mechanical properties and degree of PEI alignment on the electrode surface. The changes in surface mechanical properties were also dependent on the PEI polymer length, with higher molecular weight PEI showing different reconfiguration than the shorter polymer brushes. The study highlights that the choice of polymer material, the electrolyte composition, and CO 2 captured impact the nearelectrode environment, which has implications for CO 2 R, and presents EC-AFM as a new tool that can be used to probe the dynamic behavior of these interfaces during electrocatalysis.

36 MATERIALS SCIENCE↗

Designing polymer coatings for lithium metal protection

Abstract Protection of lithium metal has been one of the great challenges to realize a long-life, high-energy-density battery. Polymer coatings on lithium metal surface have been proven to be an effective protection method in terms of improved morphology, higher coulombic efficiency, and a longer cycle life. However, there is a variety of design principles of polymer coatings proposed by the research community, and the influence of polymer swelling in liquid electrolytes remains poorly understood. Herein we use crosslinking density and solvent–polymer interaction to quantitatively explain the mechanical property and the ion-transport property of polymer coatings when swollen in liquid electrolytes. Low crosslinking density is beneficial for reducing the rigidity and enhancing the viscosity of the polymer. Ion conductivity increases with the swelling ratio, and activation energy of lithium-ion transport increases in a polar polymer with strong ion–polymer coupling. We propose that polymer coatings must be combined with the emerging electrolytes with unconventional solvent compositions to realize a practical high-performance lithium metal battery. This study can provide design guidelines for polymer coatings through the optimized interactions with upcoming high-performance electrolytes.

Materials Science↗

Ion Conductivity and Correlations in Model Salt-Doped Polymers: Effects of Interaction Strength and Concentration

Correlated anion and cation motion can greatly reduce the overall ion conductivity in electrolytes versus the ideal conductivity calculated based on the diffusion constants alone. Using coarse-grained molecular dynamics simulations, we calculate conductivity and the degree of uncorrelated ion motion in salt-doped homopolymers and block copolymers as a function of concentration and interaction strengths. Calculating conductivity from ion mobility under an applied electric field increases accuracy versus the typical use of fluctuation dissipation relationships in equilibrium simulations. In typical electrolytes, correlation in cation-anion motion is often expected to be reduced at low ion concentrations. Yet, for these polymer electrolytes with strong ion-polymer and ion-ion interactions, we find cation-anion motion is more correlated at lower concentrations when other variables are held constant. We show this phenomenon is related to the slower ion cluster relaxation rate at low concentrations rather than the static spatial state of ion aggregation or the fraction of free ions.

36 MATERIALS SCIENCE↗

A Self-Healing, Flowable, Yet Solid Electrolyte Suppresses Li-Metal Morphological Instabilities

In this article, lithium metal (Li 0 ) solid-state batteries encounter implementation challenges due to dendrite formation, side reactions, and movement of the electrode–electrolyte interface in cycling. Notably, voids and cracks formed during battery fabrication/operation are hot spots for failure. Here, a self-healing, flowable yet solid electrolyte composed of mobile ceramic crystals embedded in a reconfigurable polymer network is reported. This electrolyte can auto-repair voids and cracks through a two-step self-healing process that occurs at a fast rate of 5.6 µm h -1 . A dynamical phase diagram is generated, showing the material can switch between liquid and solid forms in response to external strain rates. The flowability of the electrolyte allows it to accommodate the electrode volume change during Li 0 stripping. Simultaneously, the electrolyte maintains a solid form with high tensile strength (0.28 MPa), facilitating the regulation of mossy Li 0 deposition. The chemistries and kinetics are studied by operando synchrotron X-ray and in situ transmission electron microscopy (TEM). Solid-state NMR reveals a dual-phase ion conduction pathway and rapid Li + diffusion through the stable polymer-ceramic interphase. This designed electrolyte exhibits extended cycling life in Li 0 –Li 0 cells, reaching 12 000 h at 0.2 mA cm -2 and 5000 h at 0.5 mA cm -2 . Furthermore, owing to its high critical current density of 9 mA cm -2 , the Li 0 –LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) full cell demonstrates stable cycling at 5 mA cm -2 for 1100 cycles, retaining 88% of its capacity, even under near-zero stack pressure conditions.

25 ENERGY STORAGE↗

An Ultrafast, Durable, and High-Loading Polymer Anode for Aqueous Zinc-Ion Batteries and Supercapacitors

Zn metal has shown promise as an anode material for grid-level energy storage, yet is challenged by dendritic growth and low Coulombic efficiency. Herein, an ultrafast, stable, and high-loading polymer anode for aqueous Zn-ion batteries and capacitors (ZIBs and ZICs) is developed by engineering both the electrode and electrolyte. The anode polymer is rationally prepared to have a suitable electronic structure and a large pi-conjugated structure, whereas the electrolyte is manufactured based on the superiority of triflate anions over sulfate anions, as analyzed and confirmed via experiments and simulations. This dual engineering results in an optimal polymer anode with a low discharge potential, near-theoretical capacity, ultrahigh-loading capability (approximate to 50 mg cm -2 ), ultrafast rate (100 A g -1 ), and ultralong lifespan (one million cycles). Further, its mechanism involves reversible Zn 2+ /proton co-storage at the carbonyl site. When the polymer anode is coupled with cathodes for both ZIB and ZIC applications, the devices demonstrate ultrahigh power densities and ultralong lifespans, far surpassing those of corresponding Zn-metal-based devices.

25 ENERGY STORAGE↗

Three-dimensional rechargeable battery with solid-state electrolyte

A scaffold of an electrolyte is fabricated in polymer material using 3D printing techniques. A thin layer of solid electrolyte is deposited on the scaffold followed by burning off the polymer. This leaves behind a 3D foam-like solid electrolyte with two distinct non-overlapping volumes. Lithium followed by a conductive layer (for anode) is then deposited through one volume on the first surface whereas a porous or non-porous conductive layer is deposited on the opposite surface through the second volume. The non-porous conductive layer on the second surface is made porous by a selective timed etch.

Saha, Sourabh K.↗