Search NASA⌕ Search

SEARCH · Search NASA

Results for “sodium metal battery”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records

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↗

An Organic Carboxylate Host for Stable Sodium Metal Batteries

Sodium metal batteries (SMBs) hold great promise for the development of high-energy, sustainable energy storage solutions, but their practical deployment is hampered by unstable solid electrolyte interphases, uncontrollable sodium dendrite growth, and low Coulombic efficiency (CE) during repeated Na plating/stripping cycles. To address these challenges, we introduce an organic interlayer, containing perylenetetracarboxylic dianhydride sodium salt (Na4PT), on the surface of Cu current collector. This interlayer forms a sodiophilic organic interphase that lowers the nucleation barriers for sodium deposition and guides the formation of the interphase through polar carbonyl/carboxylate sites and a π-conjugated organic framework. A dendrite-free sodium metal anode is achieved using Na4PT coated Cu current collector. Under capacity-limited Na plating/stripping, Na||Na4PT@Cu half-cells deliver reversible capacities of 500 and 1,000 mAh g−1 at 0.1 and 1 A g−1 for 500 cycles with average CE above 99%. Post-cycling scanning electron microscopy and X-ray photoelectron spectroscopy measurements confirm that Na4PT@Cu promotes compact and uniform Na deposits and supports the formation of a stable interphase with reduced parasitic decomposition, directly correlating interfacial chemistry/morphology with high plating/stripping reversibility. These results highlight organic carboxylate coating as a practical interface engineering strategy for dendrite-free SMBs.

Chen, Chengxiang [University of Miami]↗

Synergetic Dual‐Additive Electrolyte Enables Highly Stable Performance in Sodium Metal Batteries

Sodium (Na)-metal batteries (SMBs) are considered one of the most promising candidates for the large-scale energy storage market owing to their high theoretical capacity (1,166 mAh g -1 ) and the abundance of Na raw material. However, the limited stability of electrolytes still hindered the application of SMBs. Herein, sulfolane (Sul) and vinylene carbonate (VC) are identified as effective dual additives that can largely stabilize propylene carbonate (PC)-based electrolytes, prevent dendrite growth, and extend the cycle life of SMBs. The cycling stability of the Na/NaNi 0.68 Mn 0.22 Co 0.1 O 2 (NaNMC) cell with this dual-additive electrolyte is remarkably enhanced, with a capacity retention of 94% and a Coulombic efficiency (CE) of 99.9% over 600 cycles at a 5 C (750 mA g -1 ) rate. The superior cycling performance of the cells can be attributed to the homogenous, dense, and thin hybrid solid electrolyte interphase consisting of F- and S-containing species on the surface of both the Na metal anode and the NaNMC cathode by adding dual additives. Such unique interphases can effectively facilitate Na-ion transport kinetics and avoid electrolyte depletion during repeated cycling at a very high rate of 5 C. This electrolyte design is believed to result in further improvements in the performance of SMBs.

25 ENERGY STORAGE↗

Tuning the solvation structure with salts for stable sodium-metal batteries

Sodium-metal batteries are an appealing, sustainable, low-cost alternative to lithium metal batteries due to the high abundance and theoretical specific capacity (1,165 mA h g -1 ) of sodium. However, the poor compatibility of the electrolyte with the cathode and anode leads to unstable electrode-electrolyte interphases. Here we introduce the concept of using a salt as a diluent, which enables the use of a single non-flammable solvent, such as trimethyl phosphate. By using sodium nitrate (NaNO 3 ) salt as a model diluent, we report a 1.1 M NaFSI-NaNO 3 -trimethyl phosphate electrolyte that forms a stable interface with sodium-metal anode. In addition, the formation of robust cathode-electrolyte interphases on Na(Ni 0.3 Fe 0.4 Mn 0.3 )O 2 cathode facilitates smooth phase transitions, thus leading to stable cycle life with a capacity retention of 80% over 500 cycles at C/5 rate in Na||Na(Ni 0.3 Fe 0.4 Mn 0.3 )O 2 cells. Further, the work demonstrates a promising approach towards the development of safe, low-cost, sustainable high-performance sodium-metal batteries. Electrolytes with non-flammable solvents are important for the safe operation of sodium-metal batteries. Here the authors report an electrolyte engineering approach, employing salts as a diluent, to enhance interfacial stability and overall safety.

25 ENERGY STORAGE↗

Non-fluorinated electrolyte for high-voltage anode-free sodium metal battery

Abundant sodium (Na) batteries are a sustainable alternative to resource-constrained lithium-ion batteries, offering huge cost advantages. However, developing high-voltage anode-free sodium metal batteries (SMBs) to narrow the energy density gap with lithium-ion batteries is hindered by a critical challenge: existing electrolytes cannot simultaneously achieve ultra-high Na coulombic efficiency and anodic stability. Here, in this study, we present a rationally designed non-fluorinated electrolyte (1.0 M NaPF 6 in 1,2-diethoxyethane/1,2-di-tert-butoxyethane) to address this key limitation, achieving Na coulombic efficiency of >99.95% and anodic stability of >4.8 V. For coin cells (2.0 mAh cm −2 , N/P = 1.7), our electrolyte design enables 4.0 V Na | |Na 3 V 2 (PO 4 ) 3 (NVP) at 5 C and 4.3 V Na | |NaNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) at 0.3 C for 5,000 and 500 cycles with a capacity retention >80%. Remarkably, the 50 mAh anode-free pouch cells 4.0 V Al | |NVP and 4.3 V Al | |NMC622 also achieve 500 and 300 cycles (retention >75%) with a specific energy of >360 Wh kg (electrode) −1 . This work focuses on electrolyte optimization and conceptual advances, whereas critical aspects such as safety, large-scale manufacturability and practical feasibility of SMBs require further investigation. The electrolyte design using non-fluorinated solvents enhances the anodic stability without sacrificing Na efficiency, laying groundwork for advancing low-cost, high-energy SMBs and supporting the transition to sustainable battery technologies.

25 ENERGY STORAGE↗

Highly Reversible Sodium Metal Battery Anodes via Alloying Heterointerfaces

As a promising pathway toward low-cost, long-duration energy storage, rechargeable sodium batteries are of increasing interest. Batteries that incorporate metallic sodium as anode promise a high theoretical specific capacity of 1166 mAh g –1 , and low reduction potential of –2.71 V. The high reactivity and poor electrochemical reversibility of sodium anodes render sodium metal anode (SMA) cells among the most challenging for practical implementation. Here, the failure mechanisms of Na anodes are investigated and the authors report that loss of morphological control is not the fundamental cause of failure. Rather, it is the inherently poor anchoring/root structure of electrodeposited Na to the electrode substrate that leads to poor reversibility and cell failure. Poorly anchored Na deposits are prone to break away from the current collector, producing orphaning and poor anode utilization. Thin metallic coatings in a range of chemistries are proposed and evaluated as SMA substrates. Based on thermodynamic and ion transport considerations, such substrates undergo reversible alloying reactions with Na and are hypothesized to promote good root growth—regardless of the morphology. Among the various options, Au stands out for its ability to support long Na anode lifetime and high reversibility (Coulombic Efficiency > 98%), for coating thicknesses in the range of 10–1000 nm. Finally, as a first step toward evaluating practical utility of the anodes, their performance in Na||SPAN cells with N:P ratio close to 1:1 is evaluated.

25 ENERGY STORAGE↗

Self‐Templated 3D Sulfide‐Based Solid Composite Electrolyte for Solid‐State Sodium Metal Batteries

Abstract Rechargeable solid‐state sodium metal batteries (SSMBs) experience growing attention owing to the increased energy density (vs Na‐ion batteries) and cost‐effective materials. Inorganic sulfide‐based Na‐ion conductors also possess significant potential as promising solid electrolytes (SEs) in SSMBs. Nevertheless, due to the highly reactive Na metal, poor interface compatibility is the biggest obstacle for inorganic sulfide solid electrolytes such as Na 3 SbS 4 to achieve high performance in SSMBs. To address such electrochemical instability at the interface, new design of sulfide SE nanostructures and interface engineering are highly essential. In this work, a facile and straightforward approach is reported to prepare 3D sulfide‐based solid composite electrolytes (SCEs), which utilize porous Na 3 SbS 4 (NSS) as a self‐templated framework and fill with a phase transition polymer. The 3D structured SCEs display obviously improved interface stability toward Na metal than pristine sulfide. The assembled SSMBs (with TiS 2 or FeS 2 as cathodes) deliver outstanding electrochemical cycling performance. Moreover, the cycling of high‐voltage oxide cathode Na 0.67 Ni 0.33 Mn 0.67 O 2 (NNMO) is also demonstrated in SSMBs using 3D sulfide‐based SCEs. This study presents a novel design on the self‐templated nanostructure of SCEs, paving the way for the advancement of high‐energy sodium metal batteries.

Guo, Xiaolin↗

Rational Electrolyte Formulation for Sodium Metal Batteries Operating in Extremely Cold Environments

Sodium metal batteries have shown considerable potential when operated at ambient temperatures. However, their performance in cold environments is constrained by increased electrolyte resistance with decreasing temperature and dendritic sodium plating associated with unstable solid electrolyte interphase (SEI), which are primarily influenced by the electrolyte composition. In this study, we present an electrolyte formulation that remains thermally stable down to −150 °C, which not only facilitates low internal resistance but also contributes to the formation of a protective SEI under cryogenic conditions. When cycled at −40 °C at 1 mA cm −2 , the sodium metal electrode exhibits a low overpotential of only 16 mV over 750 h; even at an ultra-low temperature of −80 °C, the electrode demonstrates remarkable long-term stability with a low overpotential of 54 mV sustained over 1500 h at 0.5 mA cm −2 . Furthermore, full cell evaluations when paring with Na 3 V 2 (PO 4 ) 3 cathode reveal a high average Coulombic efficiency exceeding 99.1% and a capacity retention over 83% after 100 cycles at both −40 °C and −80 °C.

Electrolyte↗

High-Voltage Sodium–Metal Batteries with Asymmetric Fluoroalkoxylated Organoborate Anion Chemistry

The high reactivity of sodium (Na) metal restricts its compatibility to ether-based electrolytes, while the poor oxidative stability of ethers precludes their coupling to high-voltage cathodes, fundamentally limiting the operating voltage and energy density of sodium–metal batteries (SMBs). We present here a coordination-asymmetry strategy to reconcile this thermodynamic mismatch by generating in situ an asymmetric fluoroalkoxylated organoborate anion, [FB(OCH(CF 3 ) 2 ) 3 ] − (BOF – ), via a Lewis acid–base adduct reaction in ether electrolyte. The asymmetric ligand architecture differentiates oxidative and fluorination pathways: oxidizable B–O moieties mediate controlled interfacial reconstruction, whereas the terminal B–F units supply fluorine for chemical passivation. This self-adaptive chemistry yields nanoscale, conformal, compositionally graded interphases: a boron-oxide/boron-oxycarbide-rich cathode-electrolyte interphase (CEI) that mitigates ether oxidation and a bilayered inorganic–organic solid–electrolyte interphase (SEI) that regulates Na deposition. The nanostructured interphases enable highly reversible Na plating/stripping with an average Coulombic efficiency (CE) of 99.98% and sustain stable 4.3 V operation of anode-free SMBs in oxidation-prone ether electrolytes. Furthermore, this work establishes asymmetric boron coordination as a molecular-level design principle for creating chemically adaptive interphases that overcome the redox asymmetry in energy-dense electrochemical systems.

Anions↗

Ultra‐Thin Single‐Particle‐Layer Sodium Beta‐Alumina‐Based Composite Polymer Electrolyte Membrane for Sodium‐Metal Batteries

Inorganic/organic composite polymer electrolytes (CPEs) with good flexibility and electrode contact have been pursued for solid-state sodium-metal batteries. However, the application of CPEs for high energy density solid-state sodium-metal batteries is still limited by the low Na + conductivity, large thickness, and low ion transference number. Herein, an ultra-thin single-particle-layer (UTSPL) composite polymer electrolyte membrane with a thickness of ≈20 µm straddled by a sodium beta-alumina ceramic electrolyte (SBACE) is presented. A ceramic Na + -ion electrolyte that bridges or percolates across an ultra-thin and flexible polymer membrane provides: 1) the strength and flexibility from the polymer membrane, 2) excellent electrolyte/electrode interfacial contact, and 3) a percolation path for Na + -ion transfer. Owing to this novel design, the obtained UTSPL-35SBACE membrane exhibits a high Na+-ion conductivity of 0.19 mS cm -1 and a transference number of 0.91 at room temperature, contributing to long-term cycling stability of symmetric sodium cells with a small overpotential. The assembled quasi-solid-state cell with the as-prepared UTSPL-35SBACE membrane displays superior cycling performance with a discharge capacity of 105 mAh g -1 at 0.5 °C rate after 100 cycles and excellent rate performance (82 mAh g -1 at 5 °C rate) at room temperature with the potassium manganese hexacyanoferrate (KMHCF)@CNTs/CNFs cathode, where KMHCF refers to potassium manganese hexacyanoferrate.

25 ENERGY STORAGE↗

Highly efficient interface stabilization for ambient-temperature quasi-solid-state sodium metal batteries

Solid-state sodium (Na) batteries (SSSBs) using sulfide-based solid electrolytes (SSEs) hold tremendous promise due to their high theoretical specific capacity, enhanced safety and abundant resources. However, detrimental interfacial issues between SSEs and Na metal present a major challenge to the advancement of sulfide-based SSSBs. To address interfacial issues, we demonstrate an efficient approach by incorporating an ionic liquid electrolyte ((PYR/Na)TFSI) as interlayer to stabilize the Na metal/SSE interface. The presence of the (PYR/Na)TFSI interlayer enables the formation of a stable solid electrolyte interphase (SEI) to prevent the harmful reactions and inhibit Na dendrites. Combination of ab initio molecular dynamics simulations and X-ray photoelectron spectroscopy revealed that this stable SEI is largely composed of reduced products of TFSI -, such as NaF and CF 3 . As a result, the symmetric cells exhibited stable Na plating/striping cycling for 300 h at 0.1 mA cm -2 . In addition, FeS2||Na quasi-solid-state batteries delivered an impressive specific capacity of over 300 mAh g -1 under the current density of 20 mA g -1 at room temperature. Under a higher current density (100 mA g -1 ), such batteries performed with long-term cycling stability and maintained a specific capacity of around 103 mAh g -1 after 330 cycles. This work demonstrates the novel perspective of using an ionic liquid interlayer to address interfacial issues, contributing to the advancement of high-performance SSSBs for the next-generation energy storage systems.

25 ENERGY STORAGE↗

Lithium‐Containing Hybrid SEI Layer Enabling High Mass Loading and Anode‐Less Sodium Metal Batteries

Abstract The continuous rupturing and rebuilding of unstable solid electrolyte interphase (SEI) layer during cycling would block Na + diffusion and induce Na dendrite formation, ultimately limiting the practical application of high‐energy‐density sodium metal batteries. Herein, a hybrid SEI layer containing Li‐species is dexterously constructed on the surface of sodium metal anode. Li‐containing inorganic components (Li 3 N, LiF, and Li 2 CO 3 ) are introduced to stabilize the Na/electrolyte interface and enhance the mechanical and diffusion kinetic properties of the SEI layer, which can reduce the side reactions and gas generation, regulate Na + flux during cycling and promote rapid Na + migration for uniform dendrite‐free Na deposition. As a result, the constructed Na symmetric cells achieve low overpotential and long cycle life of 5900, 1800, and 500 h at current densities of 3, 10, and 30 mA cm −2 , respectively. Furthermore, the full cells paired with the Na₃V₂(PO₄)₃ cathode demonstrate high specific capacity and excellent cycle stability, even at an ultra‐high cathode loading of 39.3 mg cm −2 and a low N/P ratio (negative/positive electrode capacity ratio of 1.21).

Xia, Li [State Key Laboratory of Physical Chemistr↗

Lithium‐Containing Hybrid SEI Layer Enabling High Mass Loading and Anode‐Less Sodium Metal Batteries

The continuous rupturing and rebuilding of unstable solid electrolyte interphase (SEI) layer during cycling would block Na + diffusion and induce Na dendrite formation, ultimately limiting the practical application of high-energy-density sodium metal batteries. Herein, a hybrid SEI layer containing Li-species is dexterously constructed on the surface of sodium metal anode. Li-containing inorganic components (Li 3 N, LiF, and Li 2 CO 3 ) are introduced to stabilize the Na/electrolyte interface and enhance the mechanical and diffusion kinetic properties of the SEI layer, which can reduce the side reactions and gas generation, regulate Na + flux during cycling and promote rapid Na + migration for uniform dendrite-free Na deposition. As a result, the constructed Na symmetric cells achieve low overpotential and long cycle life of 5900, 1800, and 500 h at current densities of 3, 10, and 30 mA cm −2 , respectively. Furthermore, the full cells paired with the Na₃V₂(PO₄)₃ cathode demonstrate high specific capacity and excellent cycle stability, even at an ultra-high cathode loading of 39.3 mg cm −2 and a low N/P ratio (negative/positive electrode capacity ratio of 1.21).

Diffusion kinetic↗

Metallic Cu Surface Enables Reversible Na Metal Anodes and Stabilizes Anode-Free Sodium Metal Batteries

Anode free Na metal batteries are promising for future energy storage because they not only provide the highest energy densities but also eliminate the need of handling hazardous Na metals during battery manufacturing. However, they suffer from much faster degradation due to strong sensitivities even to trace levels of side reactions. In view of the crucial roles of surface chemistry on modulating electrochemical plating, this work systematically investigated a series of Cu surfaces for Na plating and stripping in the 1.0 M NaPF 6 diglyme electrolyte. Our results suggest that Na plating and stripping on pure Cu surface without Cu oxide species exhibits much better reversibility and smaller overpotentials across a wide range of current densities, especially for the first plating/stripping cycle. The high performance includes consistently higher than 99.8% Faradaic efficiencies, much more stable interfacial resistance, and negligible formation of mossy Na after 500 cycles. This improved performance can be explained based on the stronger Na-Cu affinity compared with the Na-CuO affinity. Anode-free Na metal batteries equipped with high-capacity sodium vanadium phosphate cathodes and pure Cu current collector exhibited at least 70% capacity retention for 100 cycles.

Electrochemistry↗

Extending the low-temperature operation of sodium metal batteries combining linear and cyclic ether-based electrolyte solutions

Nonaqueous sodium-based batteries are ideal candidates for the next generation of electrochemical energy storage devices. However, despite the promising performance at ambient temperature, their low-temperature (e.g., < 0 °C) operation is detrimentally affected by the increase in the electrolyte resistance and solid electrolyte interphase (SEI) instability. Here, to circumvent these issues, we propose specific electrolyte formulations comprising linear and cyclic ether-based solvents and sodium trifluoromethanesulfonate salt that are thermally stable down to –150 °C and enable the formation of a stable SEI at low temperatures. When tested in the Na||Na coin cell configuration, the low-temperature electrolytes enable long-term cycling down to –80 °C. Via ex situ physicochemical (e.g., X-ray photoelectron spectroscopy, cryogenic transmission electron microscopy and atomic force microscopy) electrode measurements and density functional theory calculations, we investigate the mechanisms responsible for efficient low-temperature electrochemical performance. We also report the assembly and testing between –20 °C and –60 °C of full Na||Na 3 V 2 (PO 4 ) 3 coin cells. The cell tested at –40 °C shows an initial discharge capacity of 68 mAh g –1 with a capacity retention of approximately 94% after 100 cycles at 22 mA g –1 .

25 ENERGY STORAGE↗

Intrinsically sodiophilic, mesoporous metal-free wetting layers based on inexpensive carbon black for sodium-metal batteries

In this article, elevated temperature molten Na batteries are seeing a resurgence of interest for low-cost electrochemical energy storage for the grid. Of the many recent innovations in this battery concept, new methods focused on intermediate temperature operation (e.g. 110–190 °C) have gained prominence as a way to enable comparable performance with less thermal energy loss and lower-cost materials of construction. However, the poor wettability of molten Na on suitable solid-electrolyte separators such as sodium Beta Alumina Solid-Electrolyte (Na-β”-Al 2 O 3 , ‘BASE’) requires continued innovation in interface engineering to promote full utilization of the solid-electrolyte surface area and minimize cell resistance. There have been many successful approaches to improve Na-wettability to-date including heat treatment in an inert atmosphere to remove adsorbed surface species, deposition of alloying metals such as Pb, Sn, or Bi, and use of carbon-based interfacial layers. However, these approaches either lack the ability to provide good wetting at very low temperatures (near the melting point of Na) or rely on non-scalable processes and/or toxic/expensive metals. To solve these issues, a new carbon-based sodiophilic treatment is demonstrated, which utilizes inexpensive components to form a meso/macroporous sodiophilic layer, is easily applied via drop-casting or spray-coating, provides excellent wetting as low as 110 °C, and is completely metal-free. It is found that the good sodium wetting can be attributed to the wider range of pore sizes in the carbon layers demonstrated in this study. Na wetting may occur as surface tension is initially broken by larger pores, followed by the intrusion of molten Na into smaller pores due to the apparent intrinsic affinity of Na-metal for carbon surfaces, in conjunction with the capillarity effect. Low cell-level area specific resistances of 20–30 and 13–15 Ω·cm 2 are demonstrated at 110 and 140 °C respectively. Finally, the utility of this metal-free wetting layer for solid-Na anodes is explored, showing that the metal-free wetting layer can reach a critical current density of 1.88 mA·cm -2 at 30 °C.

25 ENERGY STORAGE↗