Suppressing Polysulfide Crossover in Sodium Polysulfide Redox-Flow Batteries with an Oxyanion-Functionalized Glass Fiber Separator
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Solid-state amine absorbent materials, including those containing guanidine derivatives, have received tremendous attention as the world combats the challenges of climate change.
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The 1996 Workshop was held on three consecutive days and was divided into five sessions. The first day consisted of a General Primary Battery Session and a Nickel-Hydrogen Battery On-Orbit Reconditioning Experience Focused Session. The second day consisted of a Nickel-Hydrogen Session and a Nickel-Cadmium Session. The third and final day was devoted to an Other Secondary Technologies Session which covered sodium-sulfur, nickel-zinc, nickel-metal hydride, and lithium ion technologies.
Sodium-sulfur batteries are considered to be one of the most likely battery systems for space applications. Compared with the Ni-H2 or Ni-Co battery systems, Na-S batteries offer a mass reduction by a factor of 2 to 4, representing significant launch cost savings or increased payload mass capabilities. The Na-S battery operates at between 300 and 400 C, using liquid sodium and sulfur/polysulfide electrodes and solid ceramic electrolyte; the transport of the electrode materials to the surface of the electrolyte is through wicking/capillary forces. This paper describes five tests identified for the Na-S battery flight experiment definition study, which include the cell characterization test, the reactant distribution test, the current/temperature distribution test, the freeze/thaw test, and the multicell LEO test. A schematic diagram of Na-S cell is included.
Using ai-GCMC simulations,operandoWAXS, and kinetics analysis, we found that the high-rate performance of Sb as an alloy anode in Na-ion batteries is due to the presence of an amorphous intermediate phase formed during sodiation and desodiation.
The O-type layered nickel oxides suffer from undesired cooperative Jahn–Teller distortion stemming from Ni 3+ ions and undergo multiple biphasic structural transformations during the insertion/extraction of large Na + ions, posing a significant challenge to stabilize the structural integrity. We present here a systematic investigation of the impact of substituting 5 % divalent (Mg 2+ ) or trivalent (Al 3+ or Co 3+ ) ions for Ni 3+ to alleviate Na + ion ordering and perturb the Jahn–Teller effect to enhance structural stability. Here, we gauge a fundamental understanding of the Mg−O and Na−O or Mg−O−Na bonding interactions, noting that the ionicity of the Mg−O bond deshields the electronic cloud of oxygen from Na + ions. Furthermore, calculations of the Van Vleck distortion modes reveal a relaxation of NiO 6 octahedra from Jahn–Teller distortion and a reduced electron density at the interlayer with Mg 2+ substitution. Long-range (operando X-ray diffraction) and short-range (magic angle spinning nuclear magnetic resonance) structural analyses provide insights into reduced ordering, allowing a stable continuous solid solution. Overall, Mg-substitution results in a high-capacity retention of ~96 % even after 100 cycles, showcasing the potential of this strategy for overcoming the structural instabilities and enhancing the performance of sodium-ion batteries.
The growing demand for sodium-ion batteries (SIBs) in grid storage underscores the need for electrode materials that balance performance and cost, including sustainable and robust carbon sources. The equitable and abundant distribution of materials for SIBs, along with their superior low-temperature performance, safety, and fast-charging capability, further distinguishes them from lithium-ion batteries (LIBs). Hard carbon (HC) is the state-of-the-art anode for SIBs, but current commercial HC production is localized mostly to one region of the world, raising concerns about supply chain vulnerability, critical material dependency, and environmental aspects. Here, the first demonstration of humins, an abundant biorefinery byproduct, as a precursor for HC anodes for sodium-ion storage is reported. Humins were carbonized at 1100 degrees C-1300 degrees C, and the resulting materials were subjected to comprehensive materials and electrochemical characterization. Among the temperatures studied, humins-derived hard carbon synthesized at 1200 degrees C delivers an initial reversible capacity 270mA h g-1 , with stable cycling performance up to 500 cycles and excellent rate capability, representing the optimal performance. This study establishes humins as a promising and low-cost carbon source that provides a route to mitigate supply chain risks and valorizes an underutilized biorefinery waste stream for high-performance SIB anodes.
This document contains the proceedings of the 23rd annual NASA Aerospace Battery Workshop, hosted by the Marshall Space Flight Center on November 15-19, 1992. The workshop was attended by scientists and engineers from various agencies of the U.S. Government, aerospace contractors, and battery manufacturers, as well as international participation in like kind from a number of countries around the world. The subjects covered included nickel-cadmium, nickel-hydrogen, nickel-metal hydride, and lithium based technologies, as well as advanced technologies including sodium-sulfur and various bipolar designs.
The topics covered are presented in viewgraph form and include the following: the Advanced Communications Technology Satellite; the Space Station Freedom (SSF) photovoltaic power module division; Ni/H2 battery and cell design; individual pressure vessel (IPV) nickel-hydrogen cell testing SSF support; the LeRC Electrochemical Technology Branch; improved design IPV nickel-hydrogen cells; advanced technology for IPV nickel-hydrogen flight cells; a lightweight nickel-hydrogen cell; bipolar nickel-hydrogen battery development and technology; aerospace nickel-metal hydride cells; the NASA Sodium-Sulfur Cell Technology Flight Experiment; and the lithium-carbon dioxide battery thermodynamic model.
Abstract To address the issues of limited ionic conductivity and poor interface stability at room and low temperatures in solid‐state electrolytes, a robust intrinsic ferroelectrolyte or nanoferroelectrolyte strategy for engineering solid‐state flexible ferroelectric composite electrolytes utilizing strongly coupled intrinsic ion conducting 2D/2D sodium‐rich anti‐perovskite (NaRAP)/ferroelectric perovskite heterostructures is introduced. Herein, highly scalable PVDF‐based metaferroelectrolytes with Na 2.99 Ba 0.005 OCl/Ca 2 Na 2 Nb 5 O 16 − (CNNO − ) nanosheets into a ferroelectric poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) matrix, through an in situ cross‐linking and spontaneous bridging method, for compact solid‐state sodium batteries (SSBs), are reported. Benefiting from unique well‐dispersed 3D ferroelectric coupled network and the Na 2.99 Ba 0.005 OCl/CNNO − ‐induced PVDF‐HFP ferroelectric β phase, the Na + flux is regulated, thereby inhibiting Na dendrite growth at the interface. Notably, the optimized PH‐5% NC metaferroelectrolyte exhibits rapid ion transport (1.11 × 10 −4 S cm −1 at 25 °C), a wide electrochemical window (> 4.8V), superior conformal mechanical compatibility, improved flexibility, good elasticity and flame retardancy. The solid‐state Na 3 V 2 (PO 4 ) 3 /PH‐5% NC/Na batteries present a stable cycling performance (remaining 56.4 mAh g −1 after 500 cycles at 1 C) even at 0 °C, potential for cost‐effective, safe, stable and compact SSB energy storage over 600 Wh L −1 , vastly surpassing 365 Wh L −1 of the current commercial sodium‐ion liquid‐electrolyte batteries.
Thermochemical energy storage (TCES) offers a transformative approach to address grid instability by harnessing reversible chemical reactions for efficient heat storage and release. Here, we introduce pharmaceutical organic salt hydrates as a class of materials with exceptional performance for low-grade waste heat recovery. We demonstrate ibuprofen sodium dihydrate (ISD) as an example organic hydrate exhibiting a dehydration temperature range of 60-110 °C and a remarkable dehydration enthalpy of up to 59.5 kJ/mol of water, ideally suited for capturing industrial and residential waste heat. Using rigorous multimodal characterization, including thermogravimetric analysis, differential scanning calorimetry, in-situ FTIR, in-situ PXRD, and NMR, we demonstrate ISD's superior thermal, chemical, and structural stability over 150 hydration-dehydration cycles, achieving an unprecedented cycling efficiency of ~99.9%. Compared to conventional inorganic salt hydrates like strontium chloride hexahydrate and calcium oxalate monohydrate, ISD showcases enhanced durability without deliquescence or pulverization, even under high-humidity conditions. In-situ analyses confirm the transition from ISD to ibuprofen sodium anhydrous (ISA) proceeds with structural reorganization, thereby combining the dehydration mechanism with phase transitions, resulting in higher energy storage capacity. Microstructural analyses reveal that repeated water intercalation and structural transitions aid in creating significant porosity that enhances water transport kinetics, further improving the hydration/dehydration performance. By combining the phase change and chemical dehydration mechanisms, ISD paves the way for designing a new class of organic salt hydrates, offering tunable properties to meet diverse thermal energy storage demands and supporting sustainable grid resilience.
The sodium-sulfur nonaqueous redox-flow batteries (Na-S NARFBs) using earth-abundant elements are highly attractive due to the low material cost and improved energy density for grid-scale energy storage. However, the low current performance, poor Na0/Na+ redox kinetics, and Na dendrite growth pose severe challenges. We introduce cation-diffusive layers (CDLs): thin and Na+ affinitive interlayers at the Na anode that direct Na+ transport and stabilize Na deposition. Benchmarking three archetypal materials—carbon paper (CP), glass microfiber paper (GF), and foam—across Na-Na and Na-Cu, and Na-S cells identifies CP as the optimum. CP reduces symmetric cell overpotential by more than 70%, achieves 98% Na plating-stripping efficiency, and doubles the Na-S cell current density from 0.5 to 1.0 mA cm−2 without sacrificing capacity or efficiency. Ex situ electrochemical and SEM/XPS analysis, combined with molecular dynamics (MD) studies, reveal that electron-rich carbon fibers disperse supporting salt aggregates, enrich near-surface Na+ density, and create ion transport pathways for fast Na0/Na+ exchange while mitigating membrane degradation. Because of the ion-centric mechanism, CDLs can be generalized to other metal-anode designs. Further, this work establishes CDL design rules—cationic affinity and appropriate micro/nanostructure—as a simple, scalable route to high-current, durable metal-anode flow batteries.
Sodium-ion batteries offer low-cost energy storage solutions for the grid and electric vehicles, leveraging the established "rocking-chair" Li-ion design and the natural abundance of sodium. However, SIBs face challenges such as relatively lower voltage and capacity than lithium-ion batteries, as well as dependence on nickel resources. Here, in this work, a new nickel-free cathode material, Na 0.75 Li 0.08 Cu 0.25 Mn 0.66 O 2 , was designed and synthesized. This material has a capacity of ~125 mAh/g and an average discharge voltage of 3.5 V. Notably, more than one-third of the capacity arises from lithium substitution of Cu (~8 mol.%) and high voltage activation to 4.6 V. Multimodal synchrotron x-ray characterization combining spectroscopy, microscopy, and scattering reveal the capacity is primarily from the redox of copper and oxygen, with a minor contribution from the manganese redox. Lithium substitution alters the phase transition mechanism from a two-phase transition in P3-Na 2/3 Cu 1/3 Mn 2/3 O 2 to a solid-solution in Na 0.75 Li 0.08 Cu 0.25 Mn 0.66 O 2 , enhancing the reversibility of this material.
Under the U.S. Department of Energy Office of Nuclear Energy Advanced Modeling and Simulation (NEAMS) Program, an integrated multiphysics approach is being developed to model the core bowing phenomena important to liquid metal-cooled fast reactors. Core bowing is an important passive safety mechanism in liquid metal-cooled fast reactors and involves multiphysics effects including radiation transport, fluid flow, heat transfer, and mechanical response to temperature and flux gradients. This report summarizes recent progress on developing a multiphysics, MOOSE-based workflow to predict core bowing and associated reactivity feedback. Significant new capabilities in the reactor physics code Griffin - sodium backfill and pin power reconstruction for deformed geometries - were applied in this effort. This year’s work included verification, code comparisons, sensitivity studies, and coupled demonstrations that advance the state of MOOSE-based core bowing workflow. Griffin’s sodium backfill capability was verified by demonstrating that its automated treatment of geometry expansion and material-density updates reproduces manual calculations exactly, confirming solid mass conservation and proper coolant backfilling in expanded geometries. Reconstructed pin powers were compared for Griffin’s ductheterogeneous and ring-heterogeneous treatments in single-, seven-, and nineteen-assembly cases, with best agreement observed in lower-leakage configurations and the duct-heterogeneous approach offering substantially lower computational cost. Thermal-hydraulic sensitivity sensitivities showed that MOOSE SCM, SAM, and CFD are expected to produce similar deformation predictions despite variances in their temperature predictions, and that explicit treatment of inter-assembly flow becomes increasingly important as gap flow rate increases. Finally, coupled demonstrations on small multi-assembly configurations using Griffin, MOOSE Solid Mechanics, MOOSE SCM, and Heat Conduction produced physically consistent reactivity feedback from thermal expansion and bowing. The coupled demonstrations simulated grid plate expansion as well as resultant core bowing at full power conditions. Simplifications were made in current workflow, namely the assumption of instantaneous full power conditions following hot zero power, and pre-expanding the Griffin geometry axially due to lack of an axial fuel pin expansion model and temperature feedback to Griffin.
Abstract The operation of low‐temperature electrochemical energy conversion systems (fuel cells, electrolyzers) at high pH values is of perennial interest due to the possibility of moving away from expensive platinum group metal catalysts and reducing cost. Historically, the anion exchange membranes (AEMs) and ionomers have been hampered by performance (ionic conductivity, mechanical strength) and chemical stability issues. In this context, select developments over the past decade in alternate AEM chemistries, water management methods, and production of membrane electrode assemblies (MEAs) that have enabled a significant leap in performance of alkaline fuel cells are examined. These developments are linked to performance improvements in alkaline H 2 /O 2 fuel cells and also consider developments in alkaline fuel cells using nitrogen‐containing fuels (ammonia, hydrazine), carbon‐containing fuels (alcohols, glycols), and boron‐containing fuels (sodium borohydride, ammonia borane). Finally, current challenges and bottlenecks are identified, and potential solutions are proposed.
Battery development and testing efforts at Phillips Laboratory fall into three main categories: nickel hydrogen, sodium sulfur, and solid state batteries. Nickel hydrogen work is broken down into a Low Earth Orbit (LEO) Life Test Program, a LEO Pulse Test Program, and a Hydrogen Embrittlement Investigation. Sodium sulfur work is broken down into a Geosynchronous Earth Orbit (GEO) Battery Flight Test and a Hot Launch Evaluation. Solid state polymer battery work consists of a GEO Battery Development Program, a Pulse Power Battery Small Business Innovation Research (SBIR), and an in-house evaluation of current generation laboratory cells. An overview of the program is presented.