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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Cation coordination polyhedra lead to multiple lengthscale organization in aqueous electrolytes

Understanding multiple lengthscale correlations in the pair distribution functions (PDFs) of aq. electrolytes is a persistent challenge. Here, the coordination chemistry of polyoxoanions supports an ion-network of cation-coordination polyhedra in NaNO 3(aq) and NaNO 2(aq) that induce long-range solution structure. Further, oxygen correlations associated with Na + -coordination polyhedra have two characteristics lengthscales; 3.5–5.5 Å and 5.5–7.5 Å, the latter solely associated oligomers. The PDF contraction between 5.5–7.5 Å observed in many electrolytes is attributed to the distinct O···O correlation found in dimers and dimer subunits within oligomers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Methods—Meso-Scale Electrodes for Characterizing Diffusion-Reaction Properties of Redox-Active Organics in Viscous Electrolytes

Deep Eutectic Solvents (DESs) have recently gained interest as flow battery electrolytes. Their advantages include a wider electrochemical stability window compared to aqueous electrolytes, higher solubility for redox-active species, and negligible volatility. However, DESs are often highly viscous, and suffer from low ionic conductivities. This can make assessing redox kinetics difficult when attempting to determine their viability for energy storage. In classical voltammetric measurements, low ionic conductivity manifests as high solution resistance, thereby requiring "live" compensation of the electrolyte ohmic drop when performing fast-scan voltammetry. An uncompensated or inadequately-compensated ohmic drop leads to misinterpretation of the voltammetric behavior, e.g., assessing reversibility vs. irreversibility of a redox reaction. Here, we present micro-fabricated electrodes as facile "meso-scale" electrodes, which overcome these issues by nearly eliminating the ohmic drop while retaining uniformity of the current distribution over the electrode surface. Their use in precise transport-kinetics measurements is demonstrated using a redox-active organic, i.e., 4-Hydroxy-TEMPO in an aqueous medium and in ethaline, which is a viscous DES. This study provides a methodical approach to design and to implement voltammetry experiments using meso-scale electrodes leading to reliable measurements of diffusion-reaction properties of 4-Hydroxy-TEMPO.

25 ENERGY STORAGE↗
DOE OSTI2020

An Inorganic‐Rich Solid Electrolyte Interphase for Advanced Lithium‐Metal Batteries in Carbonate Electrolytes

Abstract In carbonate electrolytes, the organic–inorganic solid electrolyte interphase (SEI) formed on the Li‐metal anode surface is strongly bonded to Li and experiences the same volume change as Li, thus it undergoes continuous cracking/reformation during plating/stripping cycles. Here, an inorganic‐rich SEI is designed on a Li‐metal surface to reduce its bonding energy with Li metal by dissolving 4 m concentrated LiNO 3 in dimethyl sulfoxide (DMSO) as an additive for a fluoroethylene‐carbonate (FEC)‐based electrolyte. Due to the aggregate structure of NO 3 − ions and their participation in the primary Li + solvation sheath, abundant Li 2 O, Li 3 N, and LiN x O y grains are formed in the resulting SEI, in addition to the uniform LiF distribution from the reduction of PF 6 − ions. The weak bonding of the SEI (high interface energy) to Li can effectively promote Li diffusion along the SEI/Li interface and prevent Li dendrite penetration into the SEI. As a result, our designed carbonate electrolyte enables a Li anode to achieve a high Li plating/stripping Coulombic efficiency of 99.55 % (1 mA cm −2 , 1.0 mAh cm −2 ) and the electrolyte also enables a Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NMC811) full cell (2.5 mAh cm −2 ) to retain 75 % of its initial capacity after 200 cycles with an outstanding CE of 99.83 %.

Liu, Sufu↗
DOE OSTI2024

Carbon capture in polymer-based electrolytes

Nanoparticle organic hybrid materials (NOHMs) have been proposed as excellent electrolytes for combined CO 2 capture and electrochemical conversion due to their conductive nature and chemical tunability. However, CO 2 capture behavior and transport properties of these electrolytes after CO 2 capture have not yet been studied. Here, we use a variety of nuclear magnetic resonance (NMR) techniques to explore the carbon speciation and transport properties of branched polyethylenimine (PEI) and PEI-grafted silica nanoparticles (denoted as NOHM-I-PEI) after CO 2 capture. Quantitative 13 C NMR spectra collected at variable temperatures reveal that absorbed CO 2 exists as carbamates (RHNCOO – or RR'NCOO – ) and carbonate/bicarbonate (CO 3 2– /HCO 3 – ). The transport properties of PEI and NOHM-I-PEI studied using 1 H pulsed-field-gradient NMR, combined with molecular dynamics simulations, demonstrate that coulombic interactions between negatively and positively charged chains dominate in PEI, while the self-diffusion in NOHM-I-PEI is dominated by silica nanoparticles. These results provide strategies for selecting adsorbed forms of carbon for electrochemical reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Modulating Solvation Structure in Concentrated Aqueous Organic Redox Flow Battery Electrolyte for Solubility and Transport Enhancement via Polycomplex Ion

Aqueous organic redox flow batteries hold great promise as a technology for creating economical grid energy storage using sustainable materials. Nonetheless, the solubility limit presents a universal barrier for all redox-active organic molecules. In this paper, a new approach is proposed to surpass the solubility limit by manipulating the solvation structure with polycomplex ion additives (PIA). Using poly(3,4-ethylenedioxythiophene) polystyrenesulfonate colloids as one example, its role in dismantling the rigid supramolecular clusters within the highly concentrated 7,8-dihydroxyphenazine-2-sulfonic acid electrolyte is investigated. 1 H and 23 Na NMR spectra and molecular dynamics simulation studies demonstrate that the bipolar structure of the PIA effectively disrupts the aggregations of DHPS and Na + ion in the highly concentrated anolyte, thus rendering a more flexible solvation structure and less restrictive ion transport, leading to substantially improved battery performance of an AORFB cell. The anolyte with PIA achieved 1.6 M and 74.3 Ah L –1 anolyte energy capacity.

25 ENERGY STORAGE↗
DOE OSTI2021

Review on Interface and Interphase Issues in Sulfide Solid-State Electrolytes for All-Solid-State Li-Metal Batteries

All-solid-state batteries have emerged as promising alternatives to conventional Li-ion batteries owing to their higher energy density and safety, which stem from their use of inorganic solid-state electrolytes instead of flammable organic liquid electrolytes. Among various candidates, sulfide solid-state electrolytes are particularly promising for the development of high-energy all-solid-state Li metal batteries because of their high ionic conductivity and deformability. However, a significant challenge remains as their inherent instability in contact with electrodes forms unstable interfaces and interphases, leading to degradation of the battery performance. In this review article, we provide an overview of the key issues for the interfaces and interphases of sulfide solid-state electrolyte systems as well as recent progress in understanding such interface and interphase formation and potential solutions to stabilize them. In addition, we provide perspectives on future research directions in this field.

25 ENERGY STORAGE↗
DOE OSTI2020

A Metal Organic Framework Derived Solid Electrolyte for Lithium–Sulfur Batteries

Lithium–sulfur batteries (LSBs) are currently considered as promising candidates for next-generation energy storage technologies. However, their practical application is hindered by the critical issue of the polysulfide-shuttle. Herein, a metal organic framework (MOF)-derived solid electrolyte is presented to address it. The MOF solid electrolyte is developed based on a Universitetet i Oslo (UIO) structure. By grafting a lithium sulfonate (-SO 3 Li) group to the UIO ligand, both the ionic conductivity and the polysulfide-suppression capability of the resulting -SO 3 Li grafted UIO (UIOSLi) solid electrolyte are greatly improved. After integrating a Li-based ionic liquid (Li-IL), lithium bis(trifluoromethanesulfonyl)imide in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, the resulting Li-IL/UIOSLi solid electrolyte exhibits an ionic conductivity of 3.3 × 10 -4 S cm -1 at room temperature. Based on its unique structure, the Li-IL/UIOSLi solid electrolyte effectively restrains the polysulfide shuttle and suppresses lithium dendritic growth. Lithium–sulfur cells with the Li-IL/UIOSLi solid electrolyte and a Li 2 S 6 catholyte show stable cycling performance that preserves 84% of the initial capacity after 250 cycles with a capacity-fade rate of 0.06% per cycle.

25 ENERGY STORAGE↗
DOE OSTI2020

Ion Exchange Gels Allow Organic Electrochemical Transistor Operation with Hydrophobic Polymers in Aqueous Solution

Conjugated-polymer-based organic electrochemical transistors (OECTs) are being studied for applications ranging from biochemical sensing to neural interfaces. While new polymers that interface digital electronics with the aqueous chemistry of life are being developed, the majority of high-performance organic transistor materials are poor at transporting biologically relevant ions. Here, the operating mode of an organic transistor is changed from that of an electrolyte-gated organic field-effect transistor (EGOFET) to that of an OECT by incorporating an ion exchange gel between the active layer and the aqueous electrolyte. This device works by taking up biologically relevant ions from solution and injecting more hydrophobic ions into the active layer. Using poly[2,5-bis(3-tetradecylthiophen-2-yl) thieno[3,2-b]thiophene] as the active layer and a blend of an ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, and poly(vinylidene fluoride-co-hexafluoropropylene) as the ion exchange gel, four orders of magnitude improvement in device transconductance and a 100-fold increase in kinetics are demonstrated. The ability of the ion-exchange-gel OECT to record biological signals by measuring the action potentials of a Venus flytrap is demonstrated. These results show the possibility of using interface engineering to open up a wider palette of organic semiconductors as OECTs that can be gated by aqueous solutions.

Bischak, Connor G.↗
DOE OSTI2020

High-Energy All-Solid-State Organic–Lithium Batteries Based on Ceramic Electrolytes

Recent studies have identified unique properties of organic battery electrode materials such as moderate redox potentials and mechanical softness which are uniquely beneficial for all-solid-state batteries based on ceramic electrolytes. Here, we further explore the promise of organic materials and demonstrate a sulfide electrolyte- based organic-lithium battery with a specific energy of 828 Wh kg –1 , rivaling the state-of- the-art of all-solid-state batteries. Two innovation steps are responsible for the accomplishment. First, the combination of lithium anode and the high-capacity cathode material pyrene-4,5,9,10-tetraone ensures a high theoretical specific energy. Second, the microstructure of the organic cathode is optimized with the introduction of cryomilling, a technique common to processing soft materials but not familiar to electrode fabrication. The cathode material utilization increases to 99.5% as a result, up from the 55–89% previously reported for ceramic electrolyte-based solid-state organic batteries. In conclusion, the improvement highlights the special requirements of solid-state organic electrodes for microstructural engineering while preserving the chemical integrity of components.

25 ENERGY STORAGE↗
DOE OSTI2020

An Inorganic-Rich Solid Electrolyte Interphase for Advanced Lithium-Metal Batteries in Carbonate Electrolytes

In carbonate electrolytes, the organic-inorganic solid electrolyte interphase (SEI) formed on the lithium (Li) metal anode surface is strongly bonded to Li and experiences the same volume change as Li, thus it undergoes continuous cracking/reformation during plating/stripping cycles. Here we report, an inorganic-rich SEI is designed on a Li metal surface to reduce its bonding energy with Li metal by dissolving 4 M concentrated LiNO 3 in dimethyl sulfoxide (DMSO) as an additive for a fluoroethylene carbonate (FEC) based electrolyte. Due to the aggregate structure of NO 3 - ions and its participation in the primary Li + solvation sheath, abundant Li 2 O, Li 3 N, and LiN x O y grains are formed in the resulting SEI, in addition to the uniform LiF distribution from the reduction of PF 6 - ions. The inorganic-rich SEI’s weak bonding (high interface energy) to Li can effectively promote Li diffusion along the SEI/Li interface and prevent Li dendrite penetration into the SEI. As a result, our designed carbonate electrolyte enables a Li anode to achieve a high Li plating/stripping CE of 99.55% (1 mA cm -2 , 1.0 mAh cm -2 ) and the electrolyte also enables a Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NMC811) full cell (2.5 mAh cm -2 ) to retain 75%of its initial capacity after 200 cycles with an outstanding CE of 99.83%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Sodium Carbazolide and Derivatives as Solid‐State Electrolytes for Sodium‐Ion Batteries

Abstract Replacing widely used organic liquid electrolytes with solid‐state electrolytes (SSEs) could effectively solve the safety issues in sodium‐ion batteries. Efforts on seeking novel solid‐state electrolytes have been continued for decades. However, issues about SSEs still exist, such as low ionic conductivity at ambient temperature, difficulty in manufacturing, low electrochemical stability, poor compatibility with electrodes, etc. Here, sodium carbazolide (Na‐CZ) and its THF‐coordinated derivatives are rationally fabricated as Na + conductors, and two of their crystal structures are successfully solved. Among these materials, THF‐coordinated complexes exhibit fast Na + conductivities, i.e., 1.20×10 −4 S cm −1 and 1.95×10 −3 S cm −1 at 90 °C for Na‐CZ‐1THF and Na‐CZ‐2THF, respectively, which are among the top Na + conductors under the same condition. Furthermore, stable Na plating/stripping is observed even over 400 h cycling, showing outstanding interfacial stability and compatibility against Na electrode. More advantages such as ease of synthesis, low‐cost, and cold pressing for molding can be obtained. In situ NMR results revealed that the evaporation of THF may play an essential role in the Na + migration, where the movement of THF creates defects/vacancies and facilitates the migration of Na + .

Yu, Yang↗
DOE OSTI2023

Sodium Carbazolide and Derivatives as Solid‐State Electrolytes for Sodium‐Ion Batteries

Abstract Replacing widely used organic liquid electrolytes with solid‐state electrolytes (SSEs) could effectively solve the safety issues in sodium‐ion batteries. Efforts on seeking novel solid‐state electrolytes have been continued for decades. However, issues about SSEs still exist, such as low ionic conductivity at ambient temperature, difficulty in manufacturing, low electrochemical stability, poor compatibility with electrodes, etc. Here, sodium carbazolide (Na‐CZ) and its THF‐coordinated derivatives are rationally fabricated as Na + conductors, and two of their crystal structures are successfully solved. Among these materials, THF‐coordinated complexes exhibit fast Na + conductivities, i.e., 1.20×10 −4 S cm −1 and 1.95×10 −3 S cm −1 at 90 °C for Na‐CZ‐1THF and Na‐CZ‐2THF, respectively, which are among the top Na + conductors under the same condition. Furthermore, stable Na plating/stripping is observed even over 400 h cycling, showing outstanding interfacial stability and compatibility against Na electrode. More advantages such as ease of synthesis, low‐cost, and cold pressing for molding can be obtained. In situ NMR results revealed that the evaporation of THF may play an essential role in the Na + migration, where the movement of THF creates defects/vacancies and facilitates the migration of Na + .

Yu, Yang↗
DOE OSTI2025

Assessing the Long-Term Stability of Anion Exchange Membranes for Electrochemical CO 2 Reduction

Materials and cell components used in CO 2 electrolysis have largely been adapted from technologies initially developed for water electrolysis and fuel cells. However, electrochemical CO 2 reduction introduces distinct material challenges due to the unique chemical environment in this process. Here, in this study, we conducted ex-situ 1000 h stability tests on commonly used anion exchange membranes, exposing them exclusively to electrolytes and organic molecules used or produced during CO 2 electrolysis, at concentrations relevant to and compatible with postseparation processes. Notably, 15% w/w n-propanol and 5 M acetic acid caused complete dissolution or partial disintegration of the membranes unless cross-linking was present and remained stable throughout the test. When the membranes stayed physically intact, most of them exhibited excellent chemical stability in alkaline medium containing alcohols or formic acid, which was confirmed by vibrational spectroscopy and ion exchange capacity measurements. However, exposure to alcohol-and acid-containing solutions led to a substantial increase in swelling and water uptake, with potential implications for mechanical stability, ion/product crossover, and compression management of adjacent components. The potential effects of CO 2 electroreduction products on membrane stability, their subsequent impact on electrolyzer performance, and mitigation strategies are discussed.

CO2RR↗
DOE OSTI2022

Practically Accessible All-Solid-State Batteries Enabled by Organosulfide Cathodes and Sulfide Electrolytes

The combination of organic electrode materials and sulfide electrolytes is expected to enable the development of all-solid-state organic batteries featuring high energy density and long-term sustainability. In this work, thiuram hexasulfide is reported as a low-cost and high-capacity organic cathode for solid-state batteries based on sulfide electrolytes, delivering a capacity of ~600 mAh g -1 and retaining 80.8 % capacity after 500 cycles. An electrochemically reversible change of the cathode interface was revealed upon cycling. Full cell displays an oscillating stress change up to 0.6 MPa during cycling, predominated by the anode side. The energy density is 1140 Wh kg -1 at the material level and 376 Wh kg -1 at the electrode level, which are among the best-reported organic cathodes to date. A high areal capacity of 10.4 mAh cm -2 is reached with a high mass loading cathode. A dry-film approach is further explored to manufacture sheet-type cells. Free-standing electrolyte film is merely ~48 μm thick and demonstrates an ultralow areal resistance of 3.9 Ω cm 2 , significantly boosts the cell-level energy density and reduces the cell internal resistance.

25 ENERGY STORAGE↗
DOE OSTI2026

Aqueous electrolyte solutions with anion-bridged secondary solvation sheaths for highly efficient zinc metal batteries

Aqueous zinc metal batteries are low-cost electrochemical devices suitable for safe grid energy storage. However, water decomposition and Zn dendrite formation detrimentally affect their coulombic efficiency. Conventional aqueous electrolyte solutions, with a concentration around 1 M, are cost-effective and exhibit high bulk ionic conductivity but cannot form a stable solid electrolyte interphase. Water-in-salt and aqueous-organic hybrid electrolyte solutions can form robust solid electrolyte interphases, but they are not kinetically efficient and cost-effective. Here, to circumvent these issues, we design variously concentrated aqueous electrolyte solutions using several salts with different donor numbers to extend anion coordination into the secondary solvation sheath. We show that salt-derived anions with donor number > 18 enter the Zn2+ first solvation sheath, and ensure a strong binding energy between the Zn2+(H2O)5-anion nanometric clusters and water molecules in the secondary solvation sheath. In particular, 2 M aqueous electrolyte solutions containing fluorinated anions exhibit bulk ionic conductivities of 26-35 mS cm−1 at 25 °C and form a ZnF2-rich solid electrolyte interphase. When tested in Zn||NaV3O8·1.5H2O Swagelok cells, the best-performing electrolyte solution enables an average coulombic efficiency of 99.99% for 1,000 cycles at 1.5 mA cm−2, corresponding to an initial specific energy of 130 Wh kg−1 (based on the combined weight of the positive and negative electrodes).

25 ENERGY STORAGE↗