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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 451 records · Page 25
All sourcesNASA NTRSDOE OSTI
NASA NTRS2006

4-Vinyl-1,3-Dioxolane-2-One as an Additive for Li-Ion Cells

Electrolyte additive 4-vinyl-1,3-dioxolane-2-one has been found to be promising for rechargeable lithium-ion electrochemical cells. This and other additives, along with advanced electrolytes comprising solutions of LiPF6 in various mixtures of carbonate solvents, have been investigated in a continuing effort to improve the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. In contrast to work by other researchers who have investigated the use of this additive to improve the high-temperature resilience of Li-ion cells, the current work involves the incorporation of 4-vinyl-1,3-dioxolane-2-one into quaternary carbonate electrolyte mixtures, previously optimized for low-temperature applications, resulting in improved low-temperature performance. The benefit afforded by 4-vinyl-1,3- dioxolane-2-one can be better understood in the light of relevant information from a number of prior NASA Tech Briefs articles about electrolytes and additives for such cells. To recapitulate: The loss of performance with decreasing temperature is attributable largely to a decrease of ionic conductivity and the increase in viscosity of the electrolyte. What is needed to extend the lower limit of operating temperature is a stable electrolyte solution with relatively small lowtemperature viscosity, a large electric permittivity, adequate coordination behavior, and appropriate ranges of solubilities of liquid and salt constituents. Whether the anode is made of graphitic or non-graphitic carbon, a film on the surface of the anode acts as a solid/electrolyte interface (SEI), the nature of which is critical to low-temperature performance. Desirably, the surface film should exert a chemically protective (passivating) effect on both the anode and the electrolyte, yet should remain conductive to lithium ions to facilitate intercalation and de-intercalation of the ions into and out of the carbon during discharging and charging, respectively. The additives investigated previously include alkyl pyrocarbonates. Those additives help to improve low-temperature performances by giving rise to the formation of SEIs having desired properties. The formation of the SEIs is believed to be facilitated by products (e.g., CO2) of the decomposition of these additives. These decomposition products are believed to react to form Li2CO3-based films on the carbon electrodes. The present additive, 4-vinyl-1,3-dioxolane-2-one, also helps to improve lowtemperature performance by contributing to the formation of SEIs having desired properties, but probably in a different manner: It is believed that, as part of the decomposition process, the compound polymerizes on the surfaces of carbon electrodes.

Smart, Marshall↗
NASA NTRS2003

Purification process for vertically aligned carbon nanofibers

Individual, free-standing, vertically aligned multiwall carbon nanotubes or nanofibers are ideal for sensor and electrode applications. Our plasma-enhanced chemical vapor deposition techniques for producing free-standing and vertically aligned carbon nanofibers use catalyst particles at the tip of the fiber. Here we present a simple purification process for the removal of iron catalyst particles at the tip of vertically aligned carbon nanofibers derived by plasma-enhanced chemical vapor deposition. The first step involves thermal oxidation in air, at temperatures of 200-400 degrees C, resulting in the physical swelling of the iron particles from the formation of iron oxide. Subsequently, the complete removal of the iron oxide particles is achieved with diluted acid (12% HCl). The purification process appears to be very efficient at removing all of the iron catalyst particles. Electron microscopy images and Raman spectroscopy data indicate that the purification process does not damage the graphitic structure of the nanotubes.

Nanotechnology/methods↗
DOE OSTI2021

New Insights into the High‐Performance Black Phosphorus Anode for Lithium‐Ion Batteries

Abstract Black phosphorus (BP) is a promising anode material in lithium‐ion batteries (LIBs) owing to its high electrical conductivity and capacity. However, the huge volume change of BP during cycling induces rapid capacity fading. In addition, the unclear electrochemical mechanism of BP hinders the development of rational designs and preparation of high‐performance BP‐based anodes. Here, a high‐performance nanostructured BP–graphite–carbon nanotubes composite (BP/G/CNTs) synthesized using ball‐milling method is reported. The BP/G/CNTs anode delivers a high initial capacity of 1375 mA h g −1 at 0.15 A g −1 and maintains 1031.7 mA h g −1 after 450 cycles. Excellent high‐rate performance is demonstrated with a capacity of 508.1 mA h g −1 after 3000 cycles at 2 A g −1 . Moreover, for the first time, direct evidence is provided experimentally to present the electrochemical mechanism of BP anodes with three‐step lithiation and delithiation using ex situ X‐ray diffraction (XRD), ex situ X‐ray absorption spectroscopy (XAS), ex situ X‐ray emission spectroscopy, operando XRD, and operando XAS, which reveal the formation of Li 3 P 7 , LiP, and Li 3 P. Furthermore, the study indicates an open‐circuit relaxation effect of the electrode with ex situ and operando XAS analyses.

Li, Minsi↗
DOE OSTI2023

Quantitative Analysis of Origin of Lithium Inventory Loss and Interface Evolution over Extended Fast Charge Aging in Li Ion Batteries

During the extreme fast charging (XFC) of lithium-ion batteries, lithium inventory loss (LLI) and reaction mechanisms at the anode/electrolyte interface are crucial factors in performance and safety. Determining the causes of LLI and quantifying them remain an essential challenge. We present mechanistic research on the evolution and interactions of aging mechanisms at the anode/electrolyte interface. We used NMC 532 /graphite pouch cells charged at rates of 1, 6, and 9 C up to 1000 cycles for our investigation. The cell components were characterized after cycling using electrochemical measurements, inductively coupled plasma optical emission spectroscopy, 7 Li solid-state nuclear magnetic resonance spectroscopy, and high-performance liquid chromatography/mass spectrometry. The results indicate that cells charged at 1 C exhibit no Li plating, and the increase of SEI thickness is the dominant source of the Li loss. In contrast, Li loss in cells charged at 9 C is related to the formation of the metallic plating layers (42%) the SEI layer (38.1%) and irreversible intercalation into the bulk graphite (19%). XPS analysis suggests that the charging rate has little influence on the evolution of SEI composition. The interactions between competing aging mechanisms were evaluated by a correlation analysis. In conclusion, the quantitative method established in this work provides a comprehensive analytical framework for understanding the synergistic coupling of anodic degradation mechanisms, forecasting SEI failure scenarios, and assessing the XFC lithium-ion battery capacity fade.

25 ENERGY STORAGE↗
DOE OSTI2021

Enhanced Performance of Pt Nanoparticles on Ni-N Co-Doped Graphitized Carbon for Oxygen Reduction Reaction in Polymer Electrolyte Membrane Fuel Cells

Since the reaction rate and cost for cathodic catalyst in polymer electrolyte membrane fuel cells are obstacles for commercialization, the high-performance catalyst for oxygen reduction reaction is necessary. The Ni encapsulated with N-doped graphitic carbon (Ni@NGC) prepared with ethylenediamine and carbon black is employed as an efficient support for the oxygen reduction reaction. Characterizations show that the Ni@NGC has a large surface area and mesoporous structure that is suitable to the support for the Pt catalyst. The catalyst structure is identified and the size of Pt nanoparticles distributed in the narrow range of 2–3 nm. Four different nitrogen species are doped properly into graphitic carbon structure. The Pt/Ni@NGC shows higher performance than the commercial Pt/C catalyst in an acidic electrolyte. The mass activity of the Pt/Ni@NGC in fuel cell tests exhibits over 1.5 times higher than that of commercial Pt/C catalyst. The Pt/Ni@NGC catalyst at low Pt loading exhibits 47% higher maximum power density than the Pt/C catalyst under H2-air atmosphere. These results indicate that the Ni@NGC as a support is significantly beneficial to improving activity.

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

Design Considerations for Fast Charging Lithium Ion Cells for NMC/MCMB Electrode Pairs

Lithium ion cells that can be quickly charged are of critical importance for the continued and accelerated penetration of electric vehicles (EV) into the consumer market. Considering this, the U.S. Department of Energy (DOE) has set a cell recharge time goal of 10–15 min. The following study provides an investigation into the effect of cell design, specifically negative to positive matching ratio (1.2:1 vs. 1.7:1) on fast charging performance. By using specific charging procedures based on negative electrode performance, as opposed to the industrial standard constant current constant voltage procedures, we show that the cells with a higher N:P ratio can be charged to ~16% higher capacity in the ten-minute time frame. Cells with a higher N:P ratio also show similar cycle life performance to those with a conventional N:P ratio, despite the fact that these cells experience a much higher irreversible capacity loss, leading to a lower reversible specific capacity.

25 ENERGY STORAGE↗
DOE OSTI2023

Gas-Phase Composition as a Predictive Metric for Calendar Life Behavior of Next-Generation Silicon Anodes

The expansion of renewable technologies and electrification of the transportation sector is driving increased demand for next-generation battery materials that provide higher power and energy density with superior cycling and calendar life stability. Silicon (Si) has a theoretical capacity nearly 10x that of graphite, and is therefore a promising anode material candidate to meet these rigorous performance demands. While leading Si anode battery demonstrations are approaching target metrics for cycle life, a series of complex and interrelated modes of reactivity lead to reduced calendar life and therefore challenge practical adoption of these materials. Deconvoluting the degradation processes that impact Si calendar life is critical to informing the rational and accelerated design of improved Si materials. In the present work, we employ novel sampling techniques and GC-MS-FID characterization to measure gas-phase composition during initial Si cycling, which we tie to selective mechanisms of Si passivation. We utilize a tiered analysis approach to identify and quantify the gas-phase reaction products associated with three advanced Si material candidates under practical operating conditions. Ex situ analysis of Si powders (pure chemical reactivity) is coupled with nondestructive in situ sampling of Si electrodes in a practical pouch-cell format (coupled chemical and electrochemical reactivity). We link the observed gas-phase species evolution to electrochemical behavior and measured calendar life of the three Si materials. Further, we evaluate the voltage-resolved evolution of gas-phase species for one such Si nanomaterial, where nonmonotonic gas generation implies competition between passivating reaction pathways. The measured gas-phase compositional data serves as a critical input for our advanced electrochemical SEI models to identify favorable vs unfavorable reaction pathways to stabilize Si. In addition to bolstering a fundamental understanding of Si reactivity, the present approach informs specific and quantifiable gas-phase metrics tied to calendar life improvements in Si, which can streamline and accelerate the process of next-generation material development.

DIRECT ENERGY CONVERSION,ENERGY STORAGE↗
NASA NTRS2013

Pt-Ni and Pt-Co Catalyst Synthesis Route for Fuel Cell Applications

Oxygen reduction reactions (ORRs) at the cathode are the rate-limiting step in fuel cell performance. The ORR is 100 times slower than the corresponding hydrogen oxidation at the anode. Speeding up the reaction at the cathode will improve fuel cell efficiency. The cathode material is generally Pt powder painted onto a substrate (e.g., graphite paper). Recent efforts in the fuel cell area have focused on replacing Pt with Pt-X alloys (where X = Co, Ni, Zr, etc.) in order to (a) reduce cost, and (b) increase ORR rates. One of these strategies is to increase ORR rates by reducing the powder size, which would result in an increase in the surface area, thereby facilitating faster reaction rates. In this work, a process has been developed that creates Pt-Ni or Pt-Co alloys that are finely divided (on the nano scale) and provide equivalent performance at lower Pt loadings. Lower Pt loadings will translate to lower cost. Precursor salts of the metals are dissolved in water and mixed. Next, the salt mixtures are dried on a hot plate. Finally, the dried salt mixture is heattreated in a furnace under flowing reducing gas. The catalyst powder is then used to fabricate a membrane electrode assembly (MEA) for electrochemical performance testing. The Pt- Co catalyst-based MEA showed comparable performance to an MEA fabri cated using a standard Pt black fuel cell catalyst. The main objective of this program has been to increase the overall efficiencies of fuel cell systems to support power for manned lunar bases. This work may also have an impact on terrestrial programs, possibly to support the effort to develop a carbon-free energy source. This catalyst can be used to fabricate high-efficiency fuel cell units that can be used in space as regenerative fuel cell systems, and terrestrially as primary fuel cells. Terrestrially, this technology will become increasingly important when transition to a hydrogen economy occurs.

Firdosy, Samad A.↗
DOE OSTI2024

Demystifying In Situ Pyrolysis Chemistry for High-Performance Polyanionic Cathodes in Sodium-Ion Batteries

In this article, the carbon coating strategy has emerged as an indispensable approach to improve the conductivity of polyanionic cathodes. However, owing to the complex reaction process between precursors of carbon and cathode, establishing a unified screening principle for carbonaceous precursors remains a technical challenge. Herein, we reveal that carbonaceous precursor pyrolysis chemistry undeniably influences the formation process and performance of Na 3 V 2 (PO 4 ) 3 (NVP) cathodes from in situ insights. By investigating three types of carbonaceous precursors, it is found that O/H-containing functional groups can provide more bonding sites for cathode precursors and generate a reducing atmosphere by pyrolysis, which is beneficial to the formation of polyanionic materials and a uniform carbon coating layer. Conversely, excessive pyrolysis of functional groups leads to a significant amount of gas, which is detrimental to the compactness of the carbon layer. Furthermore, the substantial presence of residual heteroatoms diminishes graphitization. In this case, it is demonstrated that carbon dots (CDs) precursors with suitable functional groups can comprehensively enhance the Na+ migration rate, reversibility, and interface stability of the cathode material. As a result, the NVP/CDs cathode displays outstanding capacity retention, maintaining 92% after 10,000 cycles at a high rate of 50 C. Altogether, these findings provide a valuable benchmark for carbon source selection for polyanionic cathodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Molecular Engineering to Enable High-Voltage Lithium-Ion Battery: From Propylene Carbonate to Trifluoropropylene Carbonate

Molecular engineering of electrolyte structures has led to the successful application of trifluoropropylene carbonate (TFPC), a fluorinated derivative of propylene carbonate (PC), in next-generation high-voltage high-energy lithium-ion cell. Additionally, in contrast to a PC-based electrolyte which cointercalates in the form of Li + -solvated species into the graphene layer and exfoliates a graphite anode, a TFPC-based electrolyte is highly compatible with a graphite anode at low potential. Additionally, it shows exceptional oxidation stability on the charged cathode surface owing to the presence of the -CF 3 group. An all-fluorinated electrolyte, that is, 1.0 M LiPF 6 TFPC/2,2,2-trifluoroethyl carbonate (FEMC) (1/1 volume ratio) + FEC additive, was formulated and demonstrated excellent cycling stability in a high-voltage LiNi 0.5 Mn 0.3 Co 0.2 O 2 /graphite cell cycled between 3.0 and 4.6 V.

25 ENERGY STORAGE↗
DOE OSTI2020

Translating a Material Discovery into a Commercial Product in the Modern Lithium-ion Battery Market

Lithium-ion batteries are essential for portable technology and are now poised to disrupt a century of combustion-based transportation. The electrification revolution could eliminate our reliance on fossil fuels and enable a clean energy future; advanced batteries would facilitate this transition. However, owing to the demanding performance, cost, and safety requirements, it is challenging to translate new materials from laboratory prototypes to commercial products. This Perspective describes that journey toward commercialization for a new lithium-ion battery anode material, TiNb2O7 (TNO). TNO is intended as an alternative to graphite or Li4Ti5O12 with better rate and safety characteristics than the former, and higher energy density than the latter. The high capacity of TNO stems from multielectron redox of Nb5+ to Nb3+, its operating voltage window well above Li+/Li reduction potential prevents lithium dendrite formation, and its open crystal structure leads to high-power performance. Nevertheless, the creation of a practical TNO anode was non-linear and non-trivial. Its history is built on 30 years on fundamental science that preceded its application as a battery, and its battery development included a nearly 30-year gap. The insights and lessons 2 contained in this Perspective, many of them acquired firsthand, serve two purposes: (i) to unite the disparate studies of TiNb2O7 into a coherent modern understanding relevant to its application as a battery material and (ii) to highlight some of the considerations of commercializing a new material that affect TiNb2O7 as well as new electrode candidates more generally.

Griffith, Kent J.↗
DOE OSTI2025

Coal to Carbon Fiber (C2CF) Continuous Processing for High Value Composites (Final Report)

Coal tar is a condensed and recovered by-product of the coking of metallurgical coal for steel production. The heaviest fraction of distilled coal tar is an isotropic pitch largely used as a binder in the manufacturing of carbonaceous electrodes for primary aluminum smelting and in electric arc furnaces. Coal tar pitch offers high carbon yield upon carbonization. In this project, a process to convert the domestically sourced isotropic coal tar pitch, containing very low particulates (QI = 0.32 wt.%), to form flow-domain mesophase pitch amenable for melt spinning into precursor (green) fibers for carbon fiber, was developed and optimized. The final reproducible processing developed is reviewed in this report, along with several characterizations of the mesophase pitch. A final definition of the characteristics of a ‘spinnable’ mesophase pitch is presented. With this mesophase pitch, reproducible and stable multifilament melt spinning was developed, producing green fiber tows with filament diameters of approximately 20 m. The multifilament melt spinning was the most challenging aspect of the project and required the most effort. The best practices learned from this project for melt spinning are reviewed in this report. Once spun, the green fibers were oxidatively stabilized, carbonized and graphitized under inert gas atmosphere to form the final carbon fibers. Given the relatively high softening point of the mesophase pitch, no issues of interfilament fusion were observed during batch oxidation, and subsequent batch carbonization and graphitization went smoothly in all cases. An ~ 80 wt.% conversion of the green fiber mass to final carbon fiber was achieved. After graphitization, the carbon fibers showed high tensile moduli (most were ~ 600 GPa, or 87 Msi) consistent with commercially-available high-performance pitch-based carbon fiber. However, tensile strength and strain to failure were comparatively low. Further work to reduce defects in and on the fiber surfaces would increase these properties. SEM imaging of the graphitic fiber textures is presented herein. Rudimentary composites were fabricated from the carbon fibers and characterized showing similar modulus to baseline composites fabricated with commercial carbon fiber. Finally, a basic economic analysis was done showing the potential to increase the value of the isotropic coal tar pitch by up to 13.6 to 136 times based on a carbon fiber value of $\$$5/lb to $\$$50/lb, respectively. Moreover, the site case study suggests that the coal tar from the single integrated steel mill could supply production of up to 16 kt/yr of carbon fiber. Finally, a technological gap analysis was done which shed light on remaining technical challenges. These challenges included: recovery and utilization of condensates from the mesophase pitch processing, further advancing and increasing stability of the multifilament melt spinning processing, optimization of the oxidation processing, defect reduction for increased carbon fiber strength, and the development of a weaving process towards carbon fiber fabrics. To maximize the coal value chain, the primary objectives of this project were to (a) develop and scale efficient processing technology for producing melt-spinnable mesophase pitch from isotropic coal tar pitch, (b) clarify and simplify tedious continuous fiber processing technologies (particularly multifilament melt spinning of mesophase pitch) towards the efficient production of high performance carbon fiber, and (c) demonstrate and characterize representative composite parts derived from the final carbon fiber. Immense progress was made on all 3 objectives and is detailed in this report.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

Electrolyte Regulating toward Stabilization of Cobalt-Free Ultrahigh-Nickel Layered Oxide Cathode in Lithium-Ion Batteries

Cobalt (Co)-free ultrahigh-nickel (Ni) layered oxides exhibit a double-edged competitive advantages in reducing the cathode cost and boosting the energy density, promising the sustainable development of batteries for electric vehicles. However, the increased Ni content, resultantly more highly oxidative Ni 4+ , potentially induces severe capacity fading due to the aggravated side reactions, limiting the practical applications. Here, we evaluate the compatibility of two localized high-concentration electrolytes (LHCEs) with LiNi 0.96 Mg 0.02 Ti 0.02 O 2 (NMT) cathode under a high charging voltage of 4.4 V in lithium ion batteries. The LHCE with EC additive enables the formation of stable interfacial layers on both NMT cathode and graphite anode, thus realizing a capacity retention of 97.2% over 200 cycles at 25 °C and high reversible capacities of ~180.2 and ~185.8 mAh g -1 , respectively, at 5C charge rate and 5C discharge rate. This study offers a promising approach to enable Co-free ultrahigh-Ni layered oxides for practical applications.

25 ENERGY STORAGE↗
DOE OSTI2021

A Cobalt– and Manganese–Free High–Nickel Layered Oxide Cathode for Long–Life, Safer Lithium–Ion Batteries

High-nickel LiNi 1–x–y Mn x Co y O 2 and LiNi 1–x–y Co x Al y O 2 cathodes are receiving growing attention due to the burgeoning demands on high-energy-density lithium-ion batteries. The presence of both cobalt and manganese in them, however, triggers multiple issues, including high cost, high toxicity, rapid surface deterioration, and severe transition-metal dissolution. Herein, a Co- and Mn-free ultrahigh-nickel LiNi 0.93 Al 0.05 Ti 0.01 Mg 0.01 O 2 (NATM) cathode that exhibits 82% capacity retention over 800 deep cycles in full cells, outperforming two representative high-Ni cathodes LiNi 0.94 Co 0.06 O 2 (NC, 52%) and LiNi 0.90 Mn 0.05 Co 0.05 O 2 (NMC, 60%) is presented. It is demonstrated that a titanium-enriched surface along with aluminum and magnesium as the stabilizing ions in NATM not only ameliorates unwanted side reactions with the electrolyte and structural disintegrity, but also mitigates transition-metal dissolution and active lithium loss on the graphite anode. As a result, the graphite anode paired with NATM displays an ultrathin (≈8 nm), monolayer anode-electrolyte interphase architecture after extensive cycling. Furthermore, NATM displays considerably enhanced thermal stability with an elevated exothermic temperature (213 °C for NATM vs 180 and 190 °C for NC and NMC, respectively) and remarkably reduced heat release. This work sheds light on rational compositional design to adopt ultrahigh-Ni cathodes in lithium-based batteries with low cost, long service life, and improved thermal stability.

25 ENERGY STORAGE↗
DOE OSTI2020

Titanium Niobium Oxide: From Discovery to Application in Fast-Charging Lithium-Ion Batteries

Lithium-ion batteries are essential for portable technology and are now poised to disrupt a century of combustion-based transportation. The electrification revolution could eliminate our reliance on fossil fuels and enable a clean energy future; advanced batteries would facilitate this transition. However, owing to the demanding performance, cost, and safety requirements, it is challenging to translate new materials from laboratory prototypes to industrial-scale products. This Perspective describes that journey for a new lithium-ion battery anode material, TiNb 2 O 7 (TNO). TNO is intended as an alternative to graphite or Li 4 Ti 5 O 12 with better rate and safety characteristics than the former and higher energy density than the latter. The high capacity of TNO stems from the multielectron redox of Nb 5+ to Nb 3+ , its operating voltage window well above the Li + /Li reduction potential prevents lithium dendrite formation, and its open crystal structure leads to high-power performance. Nevertheless, the creation of a practical TNO anode was nonlinear and nontrivial. Its history is built on 30 years of fundamental science that preceded its application as a battery anode, and its battery development included a nearly 30-year gap. The insights and lessons contained in this Perspective, many of them acquired firsthand, serve two purposes: (i) to unite the disparate studies of TiNb 2 O 7 into a coherent modern understanding relevant to its application as a battery material and (ii) to highlight briefly some of the challenges faced when scaling up a new material that affect TiNb 2 O 7 as well as new electrode candidates more generally.

25 ENERGY STORAGE↗
DOE OSTI2022

Facile Dual-Protection Layer and Advanced Electrolyte Enhancing Performances of Cobalt-free/Nickel-rich Cathodes in Lithium-Ion Batteries

Despite cobalt (Co)-free/nickel (Ni)-rich layered oxides being considered as one of the promising cathode materials due to their high specific capacity, their highly reactive surface is one of the shortcomings that still hinder their practical usages in high-energy-density batteries. Herein, a polyimide/polyvinylpyrrolidone (PI/PVP, denoted as PP) coating layer is demonstrated as dual-protection for LiNi 0.96 Mg 0.02 Ti 0.02 O 2 (NMT) cathode material to suppress surface contamination against moisty air and to prevent unwanted side reactions between cathode and electrolyte during electrochemical cycling. The optimal PP-coated NMT (PP@NMT) preserves a clean surface without generation of lithium (Li) residues, structural degradation, and gas evolution after exposure to air with ~30% humidity for 2 weeks. Contrarily, the exposed bare NMT shows severe contamination, structural shrinkage due to Li loss, and increased gas release during charging. In addition, the exposed PP@NMT significantly enhances the electrochemical performance of graphite (Gr)||NMT cells by decreasing byproducts and maintaining structural stability. Moreover, the exposed PP@NMT achieves a high capacity retention of 86.7% after 500 cycles in Gr||NMT cells using an advanced localized high-concentration electrolyte. Furthermore, this work demonstrates a promising facile approach to the protection of Co-free/Ni-rich layered cathodes for their practical applications even after exposure to moisty air.

25 ENERGY STORAGE↗
DOE OSTI2022

High Energy Aqueous Lithium-Ion Batteries (Final Report)

Lithium-ion batteries (LIBs) are a widely used energy storage device. For decades, researchers have been studying aqueous electrolytes due to their non-flammability and environmental friendless. However, the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) of water greatly limit the voltage window of the aqueous electrolyte. The recent concept of ‘solvent-in-salt’ electrolytes, namely ‘water-in-salt’ electrolytes (WISE) for aqueous batteries and ‘super-concentrated’ electrolytes for non-aqueous batteries, greatly expands the electrochemical window of these battery systems and consequently their energy density. This expansion occurs because the large number of salt aggregates in ‘solvent-in-salt’ electrolytes enables preferential salt decomposition over solvent decomposition to form robust interphase layers on electrodes, thus enhancing their stability in a wide range of operating voltages. However, even when the salt concentration reached 63m, regardless of cost, the cathodic potential of the WISE expanded only to 1.75V with an overall electrochemical stability window of <3.25V. To design the next generation of high energy aqueous LIBs, electrolytes that possess a wider electrochemical stability window and lower cost but still maintain the merit of non-flammability are much needed. In this project, we designed the aqueous LIBs with widened voltage window. We reported a cheap and non-flammable ternary eutectic electrolyte that can form a robust solid electrolyte interface (SEI)so that the cathodic limiting potential can be decreased to <1.5 V for Li 4 Ti 5 O 12 anodes, while maintaining both a high ionic conductivity of >10 -3 S cm –1 and a low viscosity. We demonstrated the super-stable2.5V LiMn 2 O 4 ||Li 4 Ti 5 O 12 pouch cell with mass loading of 2.5 mAh/cm. Further, LiCl-LiBr-Graphite/Li full cells were designed with high energy density. Finally, we use a bi-layer design to enlarge the voltage window of aqueous electrolyte, which can endow the stable cycling of aqueous Lithium metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Surface and Bulk Stabilization of Silicon Anodes with Mixed-Multivalent Additives: Ca(TFSI) 2 and Mg(TFSI) 2

Here, silicon is drawing attention as the upcoming anode material for the next generation of lithium-ion batteries due to its higher capacity compared to commercial graphite. However, silicon anions formed during lithiation are highly reactive with binder and electrolyte components creating an unstable SEI layer and limiting the calendar life of silicon anodes. The reactivity of lithium silicide and the formation of an unstable SEI layer is mitigated by utilizing the use of a mixture of Ca and Mg multivalent cations as an electrolyte additive for Si anodes to improve their calendar life. The effect of mixed salts on the bulk and surface of silicon anodes was studied by multiple structural characterization techniques. Ca and Mg ions in the electrolyte formed relatively thermodynamically stable quaternary Li-Ca-Mg-Si Zintl phases in an in-situ fashion and more stable and denser SEI layer on the Si particles. These in turn protect silicon particles against side reactions with electrolytes in a coin cell. The full cell with the mixed cation electrolyte demonstrates enhanced calendar life performance with lower measured current and current leakage than that of the baseline electrolyte due to reduced side reactions. Electron Microscopy, HRXRD, and solid-state NMR results showed that electrodes with mixed cations tended to have less cracking on the electrode surface compared to Si electrodes with Gen2 + FEC and the presence of mixed cations enhances cation migration and formation of quaternary Zintl phases stabilizing bulk and forming a more stable SEI.

25 ENERGY STORAGE↗