Search NASA⌕ Search

SEARCH · Search NASA

Results for “stable cycling”

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
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

A Superior Carbonate Electrolyte for Stable Cycling Li Metal Batteries Using High Ni Cathode

Li metal batteries pairing Li metal anode with high-nickel layer structured oxide cathode are a promising energy storage technology to achieve high energy density. To obtain long cycling life for Li metal batteries, the electrolyte plays a pivotal role in stabilizing both the Li metal anode and the high-nickel cathode upon electrochemical cycling. Herein, we report a carbonate electrolyte that enables a Li||LiNi 0.8 Mn 0.1 Co 0.1 O 2 pouch cell to achieve a high gravimetric energy density of 366 Wh/kg and unprecedented cycling stability with 80% capacity retention after 335 cycles. Here, the 19 F quantitative nuclear magnetic resonance spectroscopy and interface characterization demonstrate that FEC and LiDFOB can reduce the consumption rate of each other and the electrolyte, form a robust LiF-rich SEI on Li metal anode, and improve the microstructure integrity of the high-nickel cathode.

25 ENERGY STORAGE↗
DOE OSTI2025

Stable-Cycling Sustainable Na-Ion Batteries with Olivine Iron Phosphate Cathode in an Ether Electrolyte

Sustainable batteries using nontoxic, earth-abundant, and low-cost materials are key to decarbonization. Olivine NaFePO 4 fulfills these criteria, is attractive for Na-ion batteries, and can be derived from LiFePO 4 recycled from Li-ion battery wastes. Critical knowledge is needed for transforming LiFePO 4 to NaFePO 4 to enable such a sustainable, green engineering path toward high-performance Na-ion batteries. Herein, we report on the development of a stable-cycling, sustainable olivine iron phosphate-based Na-ion battery empowered by an improved understanding of materials transformation and electrolyte chemistry. First, we found that the conventional carbonate electrolyte with fluoroethylene carbonate additive causes an additional plateau (~2.4 V) at the end of the discharge process of the FePO 4 ||Na metal cell, leading to lower initial discharge capacity and voltage. This result shows that the voltage profile is influenced by not only intrinsic materials phase transformation during battery cycling but also the electrolyte additives and interphases formed. With the 1 M NaPF 6 diglyme electrolyte, we achieved an excellent capacity retention of 96% and 98% after 500 cycles at 1 and 5 C, respectively. Second, we chemically sodiated FePO 4 to form single-phase Na 0.9 FePO 4 . Na 0.9 FePO 4 ||hard carbon full cells demonstrated a remarkable capacity retention of ~84% at 3 and 5 C after 1000 cycles. The successful implementation of hard carbon, which can be derived from biomass waste, will further improve the sustainability of energy storage technologies. Our research demonstrates that electrolyte chemistry influences the voltage profile of phase-changing electrodes and provides effective electrolyte and full-cell design solutions for stable-cycling NaFePO 4 .

36 MATERIALS SCIENCE↗
DOE OSTI2020

Optimization of Graphite–SiO blend electrodes for lithium-ion batteries: Stable cycling enabled by single-walled carbon nanotube conductive additive

Lithium-alloying materials are of great interest to improve the gravimetric and volumetric energy density of lithium-ion batteries, though their associated volume fluctuation with cycling often leads to poor cycling performance. Active-inactive alloys and blending alloys with carbon materials are common strategies to accommodate volume fluctuation. Herein we set out to optimize graphite-SiO blend electrode formulations to eliminate rapid capacity fade. Electrodes with highly stable cycling were prepared by simple planetary mixing procedures, enabled by the use of just a fraction of a weight percent of commercial SWCNTs as the only conductive additive, and by the appropriate choice of binder/stabilizing agent. In fact, the use of SWCNTs allowed for graphite-free SiO electrodes with approximately 74% higher volumetric energy density relative to traditional graphite electrodes, and superior capacity retention in coin-type full-cell testing versus NMC532 cathodes.

25 ENERGY STORAGE↗
DOE OSTI2025

Stable cycling of high-mass loaded MnO 2 electrodes for sodium-ion batteries

Achieving cost-effective, sustainable solutions for large-scale energy storage are critical for advancing the global clean energy transition. In view of the challenges posed by limited lithium reserves, low-cost sodium-ion batteries (SIBs) have emerged as a promising direction, especially for grid-level energy storage. Among the various battery electrode materials, manganese dioxide (MnO 2 ) stands out as a favorable choice for such large-scale applications due to its earth abundance, cost-effectiveness, and non-toxic nature. Although MnO 2 is known as a pseudocapacitive material with superior cycling stability in aqueous electrolytes, its dissolution in non-aqueous electrolytes has restricted its use in long-lifetime batteries. In this study, we address two issues which have limited the use of MnO 2 electrodes in non-aqueous electrolytes. First, using electrochemical quartz crystal microbalance measurements in combination with other electrochemical methods, we demonstrate that diglyme (bis(2-methoxyethyl) ether) electrolyte can achieve stable cycling of electrodeposited ε-MnO 2 . These results enable us to tackle a second objective, that is increasing the mass loading of the MnO 2 electrode, since achieving high areal energy density is a significant factor in reducing manufacturing costs. Using 3D printed graphene aerogel (GA) as a scaffold, our studies show that the electrodeposited MnO 2 /GA electrodes possess scalable properties with mass loadings from 20 to 80 mg cm −2 . The resulting electrodes exhibit areal energy densities as high as 4.4 mA h cm −2 at a current density of 10 mA cm −2 . The high mass loaded MnO 2 electrodes were incorporated as a cathode in a SIB which used TiO 2 as the anode. The SIB device exhibited excellent performance with power densities in excess of 70 mW cm −2 . These studies highlight the promise of MnO 2 electrodes for use in a low-cost technology for large-scale energy storage.

25 ENERGY STORAGE↗
DOE OSTI2022

High voltage stable cycling of all-solid-state lithium metal batteries enabled by top-down direct fluorinated poly (ethylene oxide)-based electrolytes

Poly (ethylene oxide) (PEO)-based solid-state polymer electrolytes (SPEs) show prospects in all-solid-state lithium metal batteries. However, they suffer from low ionic conductivity at room temperature and interfacial instability with high voltage cathodes for long-term cycling. In this work, top-down fluorinated PEOs (F-PEOs) for the all-solid-state electrolytes, which are scalable and cost-effective, are developed to improve the battery performance. We demonstrate, that by enhancing the disordering of the F-PEO matrix, the SPE achieves a maximum Li + conductivity of 1.1 x 10 -4 S cm -1 at 40 °C, which is 20 times higher than the baseline. By forming robust cathode/SPE and Li/SPE interfaces, the F-PEO-based SPEs demonstrate stable cycling in the LiFePO 4 /Li and LiNi 0·8 Mn 0·1 Co 0·1 O 2 /Li (3-4.4 V, 500 cycles, capacity retention of 91.6%) based all-solid-state batteries at 40 °C. Therefore, our work highlights the significance of "disordering engineering" for energy storage materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Superionic conducting vacancy-rich β-Li 3 N electrolyte for stable cycling of all-solid-state lithium metal batteries

The advancement of all-solid-state lithium metal batteries requires breakthroughs in solid-state electrolytes (SSEs) for the suppression of lithium dendrite growth at high current densities and high capacities (>3 mAh cm -2 ) and innovation of SSEs in terms of crystal structure, ionic conductivity and rigidness. Here we report a superionic conducting, highly lithium-compatible and air-stable vacancy-rich β-Li 3 N SSE. This vacancy-rich β-Li 3 N SSE shows a high ionic conductivity of 2.14 × 10 -3 S cm -1 at 25 °C and surpasses almost all the reported nitride-based SSEs. A Li- and N-vacancy-mediated fast lithium-ion migration mechanism is unravelled regarding vacancy-triggered reduced activation energy and increased mobile lithium-ion population. All-solid-state lithium symmetric cells using vacancy-rich β-Li 3 N achieve breakthroughs in high critical current densities up to 45 mA cm -2 and high capacities up to 7.5 mAh cm -2 , and ultra-stable lithium stripping and plating processes over 2,000 cycles. The high lithium compatibility mechanism of vacancy-rich β-Li 3 N is unveiled as intrinsic stability to lithium metal. In addition, β-Li 3 N possesses excellent air stability through the formation of protection surfaces. All-solid-state lithium metal batteries using the vacancy-rich β-Li 3 N as SSE interlayers and lithium cobalt oxide (LCO) and Ni-rich LiNi 0.83 Co 0.11 Mn 0.06 O 2 (NCM83) cathodes exhibit excellent battery performance. Extremely stable cycling performance is demonstrated with high capacity retentions of 82.05% with 95.2 mAh g -1 over 5,000 cycles at 1.0 C for LCO and 92.5% with 153.6 mAh g -1 over 3,500 cycles at 1.0 C for NCM83. Utilizing the vacancy-rich β-Li 3 N SSE and NCM83 cathodes, the all-solid-state lithium metal batteries successfully accomplished mild rapid charge and discharge rates up to 5.0 C, retaining 60.47% of the capacity. Notably, these batteries exhibited a high areal capacity, registering approximately 5.0 mAh cm -2 for the compact pellet-type cells and around 2.2 mAh cm -2 for the all-solid-state lithium metal pouch cells.

25 ENERGY STORAGE↗
DOE OSTI2021

Multifunctional Separator Allows Stable Cycling of Potassium Metal Anodes and of Potassium Metal Batteries

Here, this is the first report of a multifunctional separator for potassium-metal batteries (KMBs). Here, double-coated tape-cast microscale AlF 3 on polypropylene (AlF 3 @PP) yields state-of-the-art electrochemical performance: symmetric cells are stable after 1000 cycles (2000 h) at 0.5 mA cm –2 and 0.5 mAh cm –2 , with 0.042 V overpotential. Stability is maintained at 5.0 mA cm –2 for 600 cycles (240 h), with 0.138 V overpotential. Postcycled plated surface is dendrite-free, while stripped surface contains smooth solid electrolyte interphase (SEI). Conventional PP cells fail rapidly, with dendrites at plating, and “dead metal” and SEI clumps at stripping. Potassium hexacyanoferrate(III) cathode KMBs with AlF 3 @PP display enhanced capacity retention (91% at 100 cycles vs 58%). AlF 3 partially reacts with K to form an artificial SEI containing KF, AlF 3 , and Al 2 O 3 phases. The AlF 3 @PP promotes complete electrolyte wetting and enhances uptake, improves ion conductivity, and increases ion transference number. The higher of K + transference number is ascribed to the strong interaction between AlF 3 and FSI – anions, as revealed through 19 F NMR. The enhancement in wetting and performance is general, being demonstrated with ester- and ether-based solvents, with K-, Na-, or Li- salts, and with different commercial separators. In full batteries, AlF 3 prevents Fe crossover and cycling-induced cathode pulverization.

NMB↗
DOE OSTI2024

Stable Cycling of Mg Metal Anodes by Regulating the Reactivity of Mg 2+ Solvation Species

Rationally designing stable nonaqueous electrolytes for Mg metal anodes demands a thorough understanding of their interfacial behaviors. Here, the critical role of cation–anion pairing in improving the cathodic stabilities of amine-based electrolytes against solvent reduction and H 2 evolution is identified. It is demonstrated that strong coordination between solvating amine groups and the Mg 2+ cation facilitates the dehydrogenation of the -NH 2 group, which is mainly responsible for low reversibility during Mg metal plating and stripping. Introducing ion-pairing into the primary solvation shell can effectively weaken the amine coordination such that its reduction is suppressed. A novel interfacial behavior regarding parasitic reaction product dissolution is also identified, which is responsible for the failure of interfacial passivation. An ion-pairing electrolyte is developed based on a weakly-solvated amine molecule and strongly coordinating Mg 2+ salt. This electrolyte composition delivers long-term Mg metal anode cycling with 99.6% Coulombic efficiency for 800 cycles.

25 ENERGY STORAGE↗
DOE OSTI2023

Chalcocarbogels as High-Capacity and Cycle-Stable Electrode Materials for Lithium and Sodium Ion Batteries

The low capacities of commercial Li ion batteries and cycle instabilities of amorphous metal sulfide based batteries impose constraints on their utilization for large-scale energy storage. We report here the acid-free, room-temperature (RT), and solution-based synthesis of a chalcogenide–carbonaceous hybrid aerogel, termed as “chalcocarbogel”, comprising molybdenum sulfide (MoS x ) and graphene oxide (GO). The chalcocarbogel is a nanoparticle-aggregated, porous, amorphous gel consisting of Mo 3 S 13 and Mo 2 S 12 -like structures as determined by synchrotron X-ray PDF, XANES, and EXAFS. The MoS x -GO chalcocarbogel demonstrates high specific capacities of ~1215 and ~807 mAh g –1 for Li/MoS x -GO and Na/MoS x -GO cells, respectively, for a 50 mAg –1 discharge rate during the first cycle. After the activation cycles, the MoS x -GO chalcocarbogel stabilizes, maintaining high specific capacities of approximately ~700 mAh g –1 for Li/MoS x -GO and ~473 mAh g –1 for Na/MoS x -GO cells, while continuously cycling. Importantly, the MoS x -GO aerogel reported here serves as a promising platform to develop chalcocarbogels for applications spanning both Li and Na ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2026

Phase Transformation Enables Stable Cycling and Fast Charging of Cation-Disordered Rocksalt Cathodes

Developing high-capacity, long-life cathodes is critical to overcome the energy limitations of current Li-ion batteries. In this work, we report a Li-excess cation-disordered rocksalt (DRX) cathode, Li 1.167 Mn0.7Ti 0.133 O 1.8 F 0.2 (M 0.7 F 0.2 ), which demonstrates excellent electrochemical performance. This cathode delivers a capacity approaching 250 mAh g –1 and maintains 200 mAh g –1 over 200 cycles with an average discharge voltage of 3.1 V at 2 V cutoff. The formation of a spinel-like phase during cycling enables fast charging, achieving over 240 mAh g –1 at 2C for 100 cycles. Combined X-ray absorption spectroscopy and transmission electron microscopy reveal reversible electrochemical redox processes and stable Mn local structures during 2 V discharge. These results highlight the potential of DRX cathodes for next-generation Li-ion batteries and provide insights into strategies to overcome kinetic limitations and optimize the cathode-electrolyte interface.

25 ENERGY STORAGE↗
DOE OSTI2023

Stable Cycling with Intimate Contacts Enabled by Crystallinity–Controlled PTFE–Based Solvent–Free Cathodes in All–Solid–State Batteries

All-solid-state batteries (ASSBs) employing Li-metal anodes and inorganic solid electrolytes are attracting great attention due to high safety and energy density for next-generation energy storage devices. However, the volume change of cathode active materials can cause contact loss, resulting in charge carrier isolation, heterogeneous current distribution, and poor electrochemical properties in ASSBs. Here, a simple, yet effective, solvent-free electrode engineering approach with polytetrafluoroethylene (PTFE) as a binder for ASSBs is reported, enabling intimate contact and stable interfaces with the cathode. It is substantiated that the crystallinity of PTFE can be controlled depending on the heat history, and highly crystalline PTFE displays robust mechanical properties. High-nickel LiNi 0.8 Mn 0.1 Co 0.1 O 2 cathode prepared with crystalline PTFE show improved cycle and rate performances in ASSBs. In addition, it is revealed that the intimate contact between cathode particles with a stable cathode electrolyte layer is maintained during cycling by postmortem studies. Furthermore, this simple engineering method can be applied to prepare cathodes with a variety of active materials and solid electrolytes in ASSBs.

25 ENERGY STORAGE↗
DOE OSTI2020

Enabling Stable Cycling of 4.2 V High-Voltage All-Solid-State Batteries with PEO-Based Solid Electrolyte

Poly(ethylene oxide) (PEO)-based solid electrolytes are expected to be exploited in solid-state batteries with high safety. Its narrow electrochemical window, however, limits the potential for high voltage and high energy density applications. In this paper, the electrochemical oxidation behavior of PEO and the failure mechanisms of LiCoO 2 -PEO solid-state batteries are studied. It is found that although for pure PEO it starts to oxidize at a voltage of above 3.9 V versus Li/Li + , the decomposition products have appropriate Li + conductivity that unexpectedly form a relatively stable cathode electrolyte interphase (CEI) layer at the PEO and electrode interface. The performance degradation of the LiCoO 2 -PEO battery originates from the strong oxidizing ability of LiCoO 2 after delithiation at high voltages, which accelerates the decomposition of PEO and drives the self-oxygen-release of LiCoO 2 , leading to the unceasing growth of CEI and the destruction of the LiCoO 2 surface. When LiCoO 2 is well coated or a stable cathode LiMn 0.7 Fe 0.3 PO 4 is used, a substantially improved electrochemical performance can be achieved, with 88.6% capacity retention after 50 cycles for Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 coated LiCoO 2 and 90.3% capacity retention after 100 cycles for LiMn 0.7 Fe 0.3 PO 4 . The results suggest that, when paired with stable cathodes, the PEO-based solid polymer electrolytes could be compatible with high voltage operation.

25 ENERGY STORAGE↗
DOE OSTI2022

Targeted masking enables stable cycling of LiNi 0.6 Co 0.2 Mn 0.2 O 2 at 4.6V

Layered LiNi x Co y Mn 1–x-y O 2 (NCM, or NCMxy(1-x-y)) is a dominant family of cathode materials for lithium-ion batteries (LIBs) due to its high energy density. Among all NCM cathode materials, NCM622 possess the optimal energy density at high potential (≥ 4.6 V vs. Li/Li + ). However, the practical application of NCM622 at high voltage (≥ 4.6 V) is limited by its parasitic reactions and associated safety concerns. Completely physical isolation has been considered as the main approach to mitigate the parasitic reaction. It has also been previously demonstrated that the interface reaction has active site selectivity, and that the reactivity of the active sites can effectively suppressed by blocking the chemically active sites. Herein, a targeted masking by LiFePO 4 @C nanoplates is reported to unlock the stable performance of NCM622 up to 4.6 V vs. Li/Li + . The (targeted masked-NCM622)|graphite pouch cell shows 86.5% capacity retention after 1000 cycles and its maximum temperature during thermal runaway is dramatically reduced from 570 °C to 415 °C. Systematic in/ex situ characterizations, first-principles calculations and half/pouch targeted LiFePO 4 @C covers the surface of NCM partcell evaluation prove that PO 4 3- is preferentially adsorbed on transition metal sites, stabilizing both the transition metal ions and oxygen ions on the surface against the ethylene carbonate-containing traditional electrolyte even under high voltage (≥ 4.6 V vs. Li/Li + ). Furthermore, this work opens up new venue for rational design of high-performance cathode materials through a low-cost and scalable decoration process, and reveal a new understanding of interfacial activity of materials.

25 ENERGY STORAGE↗
DOE OSTI2023

Toward Stable Cycling of a Cost-Effective Cation-Disordered Rocksalt Cathode via Fluorination

The recently developed Li-excess cation-disordered rock salts (DRXs) exhibit an excellent chemical diversity for the development of alternative Co/Ni-free high-energy cathodes. Herein, the synthesis of a highly fluorinated DRX cathode, Li 1.2 Mn 0.6 Ti 0.2 O 1.8 F 0.2 , based on cost-effective and earth-abundant transition metals, via a solid-state reaction, is reported. The fluorinated DRX cathode using ammonium fluoride precursor exhibits more uniform particle size and delivers a specific discharge capacity of 233 mAh g -1 and specific energy of 754 Wh kg -1 , with 206 mAh g -1 retained after 200 cycles. Further, the combined synchrotron X-ray absorption spectroscopy and resonant inelastic X-ray scattering spectroscopy analysis reveals that the remarkable cycling performance is attributed to the high fluorination and thus enhanced Mn content, enabling the utilization of more Mn redox than the oxide analog. This study demonstrates a great promise to develop next-generation cost-effective DRX cathodes with enhanced capacity retention for high-energy Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Stable Cycling of Sodium All‐Solid‐State Batteries with High‐Capacity Cathode Presodiation

Sodium all-solid-state batteries (NaSSBs) with an alloy-type anode (e.g., Sn and Sb) offer superior capacity and energy density compared to hard carbon anode. However, the irreversible loss of Na + at the alloy anode during the initial cycle results in diminished capacity and stability, impairing full-cell performance. Here, this study presents an easy-to-implement cathode presodiation strategy by employing a Na-rich material to address these challenges. Leveraging the high theoretical capacity and suitable voltage window, Na 2 S is chosen as the Na donor, which is activated by creating a mixed electron-ion conducting network, delivering a high capacity of 511.7 mAh g −1 . By adding a small amount (i.e., 3 wt.%) of Na 2 S to the cathode composite, a NaCrO 2 || Sn full cell demonstrated capacity improvement from 90.8 to 118.2 mAh g −1 (based on cathode mass). The capacity-balanced full cell can thus cycle to more than 300 times with >90% capacity retention. This work provides a practical solution to enhance the full-cell performance and advance the transformation from half-cell to full-cell applications of NaSSBs.

25 - ENERGY STORAGE↗
DOE OSTI2020

A Non‐aqueous H 3 PO 4 Electrolyte Enables Stable Cycling of Proton Electrodes

Abstract A non‐aqueous proton electrolyte is devised by dissolving H 3 PO 4 into acetonitrile. The electrolyte exhibits unique vibrational signatures from stimulated Raman spectroscopy. Such an electrolyte exhibits unique characteristics compared to aqueous acidic electrolytes: 1) higher (de)protonation potential for a lower desolvation energy of protons, 2) better cycling stability by dissolution suppression, and 3) higher Coulombic efficiency owing to the lack of oxygen evolution reaction. Two non‐aqueous proton full cells exhibit better cycling stability, higher Coulombic efficiency, and less self‐discharge compared to the aqueous counterpart.

Xu, Yunkai↗
DOE OSTI2020

A Non-aqueous H 3 PO 4 Electrolyte Enables Stable Cycling of Proton Electrodes

A non-aqueous proton electrolyte is devised by dissolving H 3 PO 4 into acetonitrile. The electrolyte exhibits unique vibrational signatures from stimulated Raman spectroscopy. Such an electrolyte exhibits unique characteristics compared to aqueous acidic electrolytes: 1) higher (de)protonation potential for a lower desolvation energy of protons, 2) better cycling stability by dissolution suppression, and 3) higher Coulombic efficiency owing to the lack of oxygen evolution reaction. Two non-aqueous proton full cells exhibit better cycling stability, higher Coulombic efficiency, and less self-discharge compared to the aqueous counterpart.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗