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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 1,693 records · Page 94
All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

Improved performance and safety of lithium ion cells with the use of fluorinated carbonate-based electrolytes

There has been increasing interest in developing lithium-ion electrolytes that possess enhanced safety characteristics, while still able to provide the desired stability and performance. Toward this end, our efforts have been focused on the development of lithium-ion electrolytes which contain partially and fully fluorinated carbonate solvents. The advantage of using such solvents is that they possess the requisite stability demonstrated by the hydrocarbon-based carbonates, while also possessing more desirable physical properties imparted by the presence of the fluorine substituents, such as lower melting points, increased stability toward oxidation, and favorable SEI film forming Characteristics on carbon. Specifically, we have demonstrated the beneficial effect of electrolytes which contain the following fluorinated carbonate-based solvents: methyl 2,2,2-trifluoroethyl carbonate (MTFEC), ethyl-2,2,2 trifluoroethyl carbonate (ETFEC), propyl 2,2,2-trifluoroethyl carbonate (PTFEC), methyl-2,2,2,2',2',2' -hexafluoro-i-propyl carbonate (MHFPC), ethyl- 2,2,2,2',2',2' -hexafluoro-i-propyl carbonate (EHFPC), and di-2,2,2-trifluoroethyl carbonate (DTFEC). These solvents have been incorporated into multi-component ternary and quaternary carbonate-based electrolytes and evaluated in lithium-carbon and carbon-LiNio.8Coo.202 cells (equipped with lithium reference electrodes). In addition to determining the charge/discharge behavior of these cells, a number of electrochemical techniques were employed (i.e., Tafel polarization measurements, linear polarization measurements, and electrochemical impedance spectroscopy (EIS)) to further characterize the performance of these electrolytes, including the SEI formation characteristics and lithium intercalatiodde-intercalation kinetics. In addition to their evaluation in experimental cells, cyclic voltammetry (CV) and conductivity measurements were performed on select electrolyte formulations to further our understanding of the trends in stability and ionic mobility imparted by different alkyl substituents in linear carbonates.

li-ion batteries fluorinated carbonate electrolyte↗
NASA NTRSDate not supplied

Broad Compatibility Study of Polymeric Materials with Ionic Silver Biocide, Part I

NASA is considering ionic silver as a residual biocide for use in potable water systems being planned for future exploration spacecraft. Compatibility of the biocide with the system’s wetted-materials of construction remains a challenge. Due to the relatively inert nature of plastics, their use in varied water system applications may offer unique opportunities to address many biocide compatibility issues. A 2020 ICES paper described a “Stage 1” assessment of several polymeric materials, in which coupons having a 2 cm 1 surface to volume ratio were exposed to solutions of 400 parts per billion (ppb) aqueous silver fluoride (AgF) for one week. In this current paper, additional Stage 1 test results are presented for select epoxies and lubricants applied on silver-inert substrates. The coupon exposure studies were also expanded to a duration of 5 weeks for the “well-behaved” Stage 1 plastics previously reported: those exhibiting silver losses above 10% and less than 50%. For this type of Stage 2 testing, silver biocide solution samples are taken from three separate (and not previously-sampled) coupon containers after 3 days, and 2, 3, 4, and 5 weeks of exposure. "Very well-behaved" Stage 1 plastics will be tested in the same manner over one year, with longer sample intervals; early-period results are included here. In addition, for select materials, the coupons were “aged” by refilling test containers with fresh AgF and observing the respective silver uptake over similar Stage 2 test durations. For all test series, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and ion-selective electrode (ISE) analyses were used to determine total and ionic silver (Ag+) concentrations, respectively. Additional sample analyses for Stage 2 tests includes total organic carbon (TOC), pH, conductivity, and oxidation-reduction potential (ORP). Ultimately, these early compatibility studies will be used to guide future material selections for developing silver biocide-compatible spacecraft water systems.

Silver Biocide↗
DOE OSTI2017

On the Use of Ionic Liquids for the Recycling of the Contaminated Material

Dealing with spent nuclear fuel (SNF) and other radioactive waste management is one of the main issues of the nuclear industry. Today, there is an increased demand for lower environmental affection and higher safety assurances within all industries dealing with radioactivity. The resulting increasing costs for dealing with radioactive waste, altogether with the pressure of public opinion, are strong motivation factors for the development of recycling schemes, softening the effects on the environment, and bringing economic advantages for the nuclear industry. This problem is even multiplied as a significant wave of decommissioning of nuclear facilities can be expected in the next decades and it makes the problem even more urgent. The Organisation for Economic Co-operation and Development/Nuclear Energy Agency estimates that 400 nuclear power plants will have to be decommissioned between 2014 and 2050 and it will generate more than 5 million tons of radioactive scrap metal. If the decommissioning of other nuclear installations is taken into account, almost 30 million tons of scrap metal contaminated by radionuclides will need to be handled?1 According to an International Atomic Energy Agency report?2 during the nuclear facility decommissioning process, only 3 % of the material is considered contaminated, but costs for its disposal can make over 60 % of overall costs. In both of mentioned areas - SNF reprocessing and material decontamination - possible benefits of ionic liquids (ILs) are studied worldwide because of their interesting physical-chemical properties and chemical behavior. ILs (described as room-temperature molten salts in older literature) are commonly described as salts with organic cations associated with organic or inorganic anions that are liquid below 373 K and fully consisting of ions and offer advantages of nonaqueous processes like a safer environment because of substituting volatile and flammable organic solvents or less serious criticality issues. At the same time, ILs beat high-temperature molten salt in comparing energy costs. Also some other of ILs' unique properties are definitely attractive for areas of SNF reprocessing and solid waste decontamination. Among other major advantages of ionic liquids, negligible vapor pressure, non-flammability, chemical and mechanical stability, tunability as well as good electric conductivity or wide electrochemical window are usually being mentioned. In this contribution, the experimental verification of some principles needed for the development of the decontamination of material contaminated with uranium and europium are presented as model cases.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Mixed Ionic–Electronic Conductor of Perovskite Li x La y MO 3-δ toward Carbon-Free Cathode for Reversible Lithium–Air Batteries

Mixed ionic–electronic conductors (MIECs) can play a pivotal role in achieving high energies and power densities in rechargeable batteries owing to their ability to simultaneously conduct ions and electrons. In our study, a new strategy is proposed wherein late 3d transition metals (TMs) are substituted into a perovskite Li-ion conductor to transform it into a Li-containing MIEC. First-principles calculations show that perovskite Li x La y MO 3 with late 3d TMs have a low oxygen vacancy formation energy, implying high electron carrier concentrations corresponding to high electronic conductivity. The activation barriers for Li diffusion in Li x La y MO 3 (M = Ti, Cr, Mn, Fe, and Co) are below 0.411 eV, resulting in high Li-ion conductivity. The designed perovskites of Li0.34La 0.55 MnO 3-δ experimentally prove to have high electronic (2.04 × 10 -3 S cm -1 ) and Li-ion (8.53 × 10 -5 S cm -1 ) conductivities, and when applied in a carbon-free cathode of a Li–air cell, they deliver superior reversibility at 0.21 mAh cm -2 over 100 charge/discharge cycles while avoiding the degradation associated with carbonaceous materials. Finally, this strategy enables the effective design of Li-conducting MIEC and reversible Li–air batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Proton Conducting Neuromorphic Materials and Devices

Neuromorphic computing and artificial intelligence hardware generally aims to emulate features found in biological neural circuit components and to enable the development of energy-efficient machines. In the biological brain, ionic currents and temporal concentration gradients control information flow and storage. It is therefore of interest to examine materials and devices for neuromorphic computing wherein ionic and electronic currents can propagate. Protons being mobile under an external electric field offers a compelling avenue for facilitating biological functionalities in artificial synapses and neurons. In this review, we first highlight the interesting biological analog of protons as neurotransmitters in various animals. We then discuss the experimental approaches and mechanisms of proton doping in various classes of inorganic and organic proton-conducting materials for the advancement of neuromorphic architectures. Since hydrogen is among the lightest of elements, characterization in a solid matrix requires advanced techniques. We review powerful synchrotron-based spectroscopic techniques for characterizing hydrogen doping in various materials as well as complementary scattering techniques to detect hydrogen. First-principles calculations are then discussed as they help provide an understanding of proton migration and electronic structure modification. Outstanding scientific challenges to further our understanding of proton doping and its use in emerging neuromorphic electronics are pointed out.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Holistic design principles for flow batteries: Cation dependent membrane resistance and active species solubility

Cation dependent resistance of a commercial cation exchange membrane, Nafion™ 212, as well as the solubility of select active materials are investigated, demonstrating practical consequences of cation choice on redox flow battery (RFB) performance. The conductivity of alkali and methyl- or -alcohol substituted ammonium cations through pretreated Nafion™ 212 reveal that cation size is the dominant factor affecting ionic transport. Among the alkali series the resistance increases with larger ionic radii and similarly, with increasing steric bulk through substitution on ammonia. The solubility of ferrocyanide, a commonly used redox flow battery posolyte (or catholyte), as well as iron, cobalt, and chromium metal-organic compounds are determined for the same series of cations. Full cells are assembled using various cation mixtures and membrane pre-treatments to demonstrate practical effects of each variable. Here, we highlight the need to carefully select the correct cations for efficient electrolyte design, since certain cations may lead to high conductivity but low solubility, or vice versa, and provide design principles for RFBs using Nafion™ 212.

25 ENERGY STORAGE↗
DOE OSTI2024

Side chain engineering in indacenodithiophene- co -benzothiadiazole and its impact on mixed ionic–electronic transport properties

Organic semiconductors are increasingly being decorated with hydrophilic solubilising chains to create materials that can function as mixed ionic–electronic conductors, which are promising candidates for interfacing biological systems with organic electronics. While numerous organic semiconductors, including p- and n-type materials, small molecules and polymers, have been successfully tailored to encompass mixed conduction properties, common to all these systems is that they have been semicrystalline materials. Here, we explore how side chain engineering in the nano-crystalline indacenodithiophene-co-benzothiadiazole (IDTBT) polymer can be used to instil ionic transport properties and how this in turn influences the electronic transport properties. This allows us to ultimately assess the mixed ionic–electronic transport properties of these new IDTBT polymers using the organic electrochemical transistor as the testing platform. Using a complementary experimental and computational approach, we find that polar IDTBT derivatives can be infiltrated by water and solvated ions, they can be electrochemically doped efficiently in aqueous electrolyte with fast doping kinetics, and upon aqueous swelling there is no deterioration of the close interchain contacts that are vital for efficient charge transport in the IDTBT system. Despite these promising attributes, mixed ionic–electronic charge transport properties are surprisingly poor in all the polar IDTBT derivatives. Albeit a “negative” result, this finding clearly contradicts established side chain engineering rules for mixed ionic–electronic conductors, which motivated our continued investigation of this system. We eventually find this anomalous behaviour to be caused by increasing energetic disorder in the polymers with increasing polar side chain content. We have investigated computationally how the polar side chain motifs contribute to this detrimental energetic inhomogeneity and ultimately use the learnings to propose new molecular design criteria for side chains that can facilitate ion transport without impeding electronic transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Impact of pore size, interconnections, and dynamic conductivity on the electrochemistry of vanadium pentoxide in well defined porous structures

Considering the tortuous, random porous nanostructures existing in many battery electrodes, it is essential to understand electronic and ionic behaviors in such a confined nanoscale porous geometry in which electron and ion transports can change dynamically. Here, we have carefully designed three dimensional (3D) interconnected porous electrode structures and performed experiments to probe how the ion and electron transport is impacted within these controlled geometries. By using anodized aluminum oxide as a template, we were able to fabricate both 1D array electrodes and 3D electrodes with varying numbers of interconnections, utilizing vanadium oxide (V 2 O 5 ) as the active material. We demonstrate that the inherent properties of the electrode material in combination with the structural properties of the electrodes can both positively and negatively impact electrochemical characteristics. Most notably, electrodes with seven interconnecting layers in their structure had 19.7% less capacity at 25C than electrodes with zero interconnecting layers, demonstrating the negative effect of interconnections combined with poor electronic conductivity of V 2 O 5 upon lithiation beyond one Li insertion. These results indicate that a careful consideration of the material and structural properties is needed for the design of high performance battery systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Exploring the Use of Ionic Liquid Mixtures to Enhance the Performance of Dicationic Ionic Liquids

Dicationic ionic liquids (DILs) of diverse structural architectures (including symmetrical and asymmetrical ammonium, phosphonium and heterodications and the bis(trifluoromethylsulfonyl)amide (NTf 2 - ) anion) have been prepared and used as additives to N-methyl-N-ethoxyethylpyrrolidinium (P 1 EOE) NTf 2 , a relatively high-performing IL in terms of its transport properties (viscosity 53 mPa s). The three-ion, binary IL mixtures were characterized for their thermal and transport properties using differential scanning calorimetry, temperature dependent viscosity, conductivity and Pulsed Gradient Spin Echo (PGSE) NMR. Variable temperature 1 H, 19 F and 31 P self-diffusion coefficients were determined at 25, 60 and 75°C. The order of the diffusion coefficients was D(P 1 EOE + ) > D(anion) > D(dication), and the composition of the dication had a strong effect on the degree to which diffusion of all three species is more or less coupled. IL mixtures containing about 30 mol % of the dicationic NTf 2 and 70 mol % of P 1 EOE NTf 2 resulted in a significant decrease in glass transition temperatures and viscosities compared to the pure DIL. The mixtures extended the liquid range and potential for practical applications significantly. Finally, the data obtained here provides insight into the future design of dicationic salts tailored to exhibit lower viscosity and higher conductivities.

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

Multi-Sourced Collaboration for the Production and Refining of Rare Elements and Critical Metals (Final Technical Report)

The project objective was to develop a feasible and cost-effective method for recovering rare earth elements (REEs) and critical materials (CMs) from coal and coal byproducts, resulting in high-purity individually separated REEs and CMs. The targeted REEs included Y, Pr, Nd, Gd, Dy, and Sm, with a purity of over 99.5%, while the CMs included Co, Mn, Ga, Sr, Li, Ni, Zn, and Ge, with a purity of over 90%. The project aimed to design a prototype facility capable of producing 1-3 tonnes/day of high-purity REO mixes. The work was divided into four designated circuits: 1) REE extraction and concentration, 2) REE separation and purification, 3) RE metal production, and 4) CM production. To achieve these goals, the project involved 11 tasks, including technology reviews, research, process flow diagram development, mass balance estimation, and preliminary technical-economic analysis. The project team included researchers from the University of Kentucky, University of Alabama and Virginia Tech as well as process specialists from Argonne National Laboratory. MP Materials provided technical support regarding rare earth markets and processing while Alliance Coal performed resource assessment. The project included a market analysis for Nd/Pr, Tb, Dy, Gd, Y, Co, Mn, Li, Sr, Ga, Ni, Zn, and Ge. These analyses provided insights into the supply and demand trends as well as historic and future projections of market price relative to purity requirements for these elements. Two coal resources were selected for the project: the West Kentucky No. 13 (Baker) Seam and an undisclosed lignite resource in the Illinois coal basin. The estimated quantities of REEs in these resources were calculated based on production samples and drilling data. It was estimated that there is adequate supply for an operation producing one metric ton daily of higher purity mixed rare earth oxides (MREO) for approximately 20 years at a site located in western Kentucky. In Circuit 1, project data was obtained from a pilot heap leach and REE concentration facility. It was concluded that the existing circuit, which generated a MREO concentrate, two types of CM mixed products, and Li- and Sr-containing waters, would be suitable feed for circuits 2-4. Data from the first-of-its-kind coal coarse refuse heap leach pilot pad played a crucial role in estimating reliable elemental concentrations of the pregnant leaching solution (PLS). The average total REE concentration in the PLS was found to be 28.6 ppm. In Circuit 2, several concepts were explored including a novel process referred to as solvent-assisted chromatography (SAC). This concept involved a novel columnar reactor that incorporated multiple mixer/settlers, thereby enabling the operation of counter-flowing aqueous and organic phases. Unfortunately, due to project time constraints, a complete fundamental modeling analysis could not be completed to fully evaluate the technology. Molten salt electrowinning was considered as an alternative for circuit 3 following circuit 2 purification circuit utilizing the novel SAC process. A mass and energy balance of Nd reduction to metal in a fluoride containing molten salt electrolyte was conducted. Comparisons were made with the current state of Asian molten salt electrorefining, and potential improvements in siphoning rare earth metals (REM) from the reactor were presented. A cost estimate was performed for the production of 1 tonne per day, which yielded a total of $2.29 million for the nine electrowinning (EW) cells required. The selected option for circuits 2 and 3 was a plasma distillation process, which initially separates rare earth elements (REEs) from other elements. This is followed by selective electrowinning in various ionic liquids. The selection was made on the basis of thermodynamic modeling and experimental data previously published by a project partner. The combination offers an innovative approach to integrated refining and RE metal production. For Circuit 4, an extensive literature review was conducted for the processing of the CMs. The ultimate decision was to utilize a combined plasma and ionic liquid process as well to produce individual high-purity concentrates of Zn, Ni, Co, Mn, and Mg. A separate flowsheet for Li and Sr was recommended, which would yield carbonates of these elements. Due to the lack of suitable experimental data at this time, a process recommendation could not be provided but several methods have been proposed for consideration. Lastly, a techno-economic analysis (TEA) was conducted to assess the effectiveness of the proposed process for further investigation. The TEA results revealed a capital expense (CapEx) of $737 million and an annual operational expense (OpEx) of $220 million. Due to the selected elements, the hypothetical heap leach pad can produce 1 metric tonne per day of REO equivalent, but a conscious decision was made to only treat targeted REEs, resulting in the production of 0.4 metric tonne of REM. An estimated annual revenue of $90.87 million was projected based on standard market pricing information provided by the funding agency. During the TEA, ten different modules were evaluated for costing purposes. The precipitation circuit was identified as the largest single operational expense, followed by the Mg/Mn process due to the amount of treated metal. In terms of capital expenditures, the heap leach process incurred the highest cost, followed by the Mg/Mn process. The scalability of the plasma process is a crucial consideration since the reactors cannot be scaled beyond the largest demonstrated size due to their reliance on surface area of the slag and vapor phase. The purity estimate for the REEs are generally 98%±2% to produce a metal. The purity level being lower than the project objective was due to the lack of specific experimental data needed to tighten the tolerance of the estimates. Based on literature and previous experience, the CMs are estimated as follows; Ga (95%+, metal), Sr (95%+, carbonate), Li (95%+, carbonate), Ni (98%±2%, metal), Zn (95%+, metal sponge), Ge (95%+, metal), Co (98%±2%, metal), and Mn (98%±2%, metal).

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS1984

Electrical conductivity studies on CuBr containing Al2O3 particles

The conductivity of CuBr was studied and the role of a second phase, Al2O3, dispersed in CuBr was tested. CuBr melts at 493 C and exhibits three phases in the solid state. CuBr is a good ionic conductor with a transport number for copper ions of virtually unity with weighed proportions of the appropriate chemicals used. The CuBr materials were heated above melting point of CuBr, and the samples were sandwiched between copper electrodes. The ac conductivity, was determined at 1 kHz between 25 and 440 C depending on the sample. It was shown that at low temperatures, the conductivity for CuBr (Al2O3) increased by as much as 100, whereas in the beta phase the conductivity of CuBr containing Al2O3 decreased. The electrical conductivity studies are in agreement with earlier data.

Dubec, P. M.↗
DOE OSTI2017

Pore network modeling of the electrical signature of solute transport in dual-domain media: Dual-Domain Electrical Signature

Dual-domain models are used to explain anomalous solute transport behavior observed in diverse hydrologic settings and applications, from groundwater remediation to hyporheic exchange. To constrain such models, new methods are needed with sensitivity to both immobile and mobile domains. Recent experiments indicate that dual-domain transport of ionic tracers has an observable geoelectrical signature, appearing as a nonlinear, hysteretic relation between paired bulk and fluid electrical conductivity. Here in this paper we present a mechanistic explanation for this geoelectrical signature and evaluate assumptions underlying a previously published petrophysical model for bulk conductivity in dual-domain media. Pore network modeling of fluid flow, solute transport, and electrical conduction (1) verifies the geoelectrical signature of dual-domain transport, (2) reveals limitations of the previously used petrophysical model, and (3) demonstrates that a new petrophysical model, based on differential effective media theory, closely approximates the simulated bulk/fluid conductivity relation. These findings underscore the potential of geophysically based calibration of dual-domain models.

58 GEOSCIENCES↗
DOE OSTI2023

Direct Insertion Polymerization of Ionic Monomers: Rapid Production of Anion Exchange Membranes

Abstract The limited number of methods to directly polymerize ionic monomers currently hinders rapid diversification and production of ionic polymeric materials, namely anion exchange membranes (AEMs) which are essential components in emerging alkaline fuel cell and electrolyzer technologies. Herein, we report a direct coordination‐insertion polymerization of cationic monomers, providing the first direct synthesis of aliphatic polymers with high ion incorporations and allowing facile access to a broad range of materials. We demonstrate the utility of this method by rapidly generating a library of solution processable ionic polymers for use as AEMs. We investigate these materials to study the influence of cation identity on hydroxide conductivity and stability. We found that AEMs with piperidinium cations exhibited the highest performance, with high alkaline stability, hydroxide conductivity of 87 mS cm −1 at 80 °C, and a peak power density of 730 mW cm −2 when integrated into a fuel cell device.

Hsu, Jesse H.↗
DOE OSTI2023

Direct Insertion Polymerization of Ionic Monomers: Rapid Production of Anion Exchange Membranes

The limited number of methods to directly polymerize ionic monomers currently hinders rapid diversification and production of ionic polymeric materials, namely anion exchange membranes (AEMs) which are essential components in emerging alkaline fuel cell and electrolyzer technologies. Herein, we report a direct coordination-insertion polymerization of cationic monomers, providing the first direct synthesis of aliphatic polymers with high ion incorporations and allowing facile access to a broad range of materials. We demonstrate the utility of this method by rapidly generating a library of solution processable ionic polymers for use as AEMs. We investigate these materials to study the influence of cation identity on hydroxide conductivity and stability. Furthermore, we found that AEMs with piperidinium cations exhibited the highest performance, with high alkaline stability, hydroxide conductivity of 87 mS cm –1 at 80 °C, and a peak power density of 730 mW cm –2 when integrated into a fuel cell device.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Sustainion Imidazolium‐Functionalized Polymers for Carbon Dioxide Electrolysis

Abstract CO 2 electrolysis is a key step in CO 2 conversion into fuels and chemicals as a way of mitigating climate change. We report the synthesis and testing of a series of new anion‐conductive membranes (tradenamed Sustainion™) for use in CO 2 electrolysis. These membranes incorporate the functional character of imidazolium‐based ionic liquids as co‐catalysts in CO 2 reduction into a solid membrane with a styrene backbone. We find that the addition of an imidazolium group onto the styrene side‐chains increases the selectivity of the reaction from approximately 25 % to approximately 95 %. The current at 3 V is increased by a factor of 14. So far we have been able to tune these parameters to achieve stable cells that provide current densities higher than 100 mA cm −2 at 3 V cell potential with a CO product selectivity over 98 %. Stable performance was observed for 6 months of continuous operation (>150 000 000 turnovers). These results demonstrate that imidazolium polymers are ideal membranes for CO 2 electrolysis.

Kutz, Robert B.↗
DOE OSTI2018

Electrochemical Energy Storage with an Aqueous Quinone–Air Chemistry

We present that organic electrode materials such as quinones are drawing rising attention as promising redox-active materials for the development of rechargeable batteries. In aqueous solutions, the redox potential of quinones is dependent on the alkalinity and acidity of the medium. Under an alkaline condition, the oxidation potential of hydroquinone (existing as diphenolate) is ca. 0.8 V lower than that under an acidic condition. On the other hand, under an acidic condition, the reduction potential of oxygen is ca. 0.8 V higher than that under an alkaline condition. By taking these advantages, a Quinone-air cell with a rational voltage is strategically demonstrated with an alkaline anode electrolyte and an acidic cathode electrolyte, which are physically separated by a Na + -ion conductive solid-state electrolyte membrane. Finally, the Na + -ions shuttling through the solid-state membrane act as ionic media-tors/messengers to sustain and link the redox reactions at the two electrodes.

25 ENERGY STORAGE↗
DOE OSTI2016

Stable electrolyte for high voltage electrochemical double-layer capacitors

A simple electrolyte consisting of NaPF 6 salt in 1,2-dimethoxyethane (DME) can extend the voltage window of electric double-layer capacitors (EDLCs) to >3.5 V. DME does not passivate carbon electrodes at very negative potentials (near Na/Na + ), extending the practical voltage window by about 1.0 V compared to standard, non-aqueous electrolytes based on acetonitrile. The voltage window is demonstrated in two- and three-electrode cells using a combination of electrochemical impedance spectroscopy (EIS), charge-discharge cycling, and measurements of leakage current. DME-based electrolytes cannot match the high conductivity of acetonitrile solutions, but they can satisfy applications that demand high energy density at moderate power. The conductivity of NaPF 6 in DME is comparable to commercial lithium-ion battery electrolytes and superior to most ionic liquids. Lastly, factors that limit the voltage window and EDLC energy density are discussed, and strategies to further boost energy density are proposed.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2018

Operando STM study of the interaction of imidazolium-based ionic liquid with graphite

Understanding interactions at the interfaces of carbon with ionic liquids (ILs) is crucially beneficial for the diagnostics and performance improvement of electrochemical devices containing carbon as active materials or conductive additives in electrodes and ILs as solvents or additives in electrolytes. The interfacial interactions of three typical imidazolium-based ILs, 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (AMImTFSI) ILs having ethyl (C 2 ), butyl (C 4 ) and octyl (C 8 ) chains in their cations, with highly oriented pyrolytic graphite (HOPG) were studied in-situ by electrochemical scanning tunneling microscopy (EC-STM). The etching of HOPG surface and the exfoliation of graphite/graphene flakes as well as cation intercalation were observed at the HOPG/C 2 MImTFSI interface. The etching also takes place in C 4 MImTFSI at -1.5 V vs Pt but only at step edges with a much slower rate, whereas C 8 MIm + cations adsorbs strongly on the HOPG surface under similar conditions with no observable etching or intercalation. Finally, the EC-STM observations can be explained by the increase in van der Waals interaction between the cations and the graphite surface with increasing length of alkyl chains.

25 ENERGY STORAGE↗