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Results for “non-aqueous electrolytes”

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Solvent independent reference electrodes for use with non-aqueous electrolytes

The present disclosure relates to a method for forming a reference electrode for use in electrochemical testing applications. The method may involve positioning a porous frit against one end of a hollow tube, and securing the frit and the hollow tube to one another to form an assembly. The method may further involve forming a silver sulfide coating on a silver wire to produce a silver sulfide coated silver wire. The method may further involve filling the hollow tube with a non-aqueous solution, and inserting at least a portion of the silver sulfide coated silver wire into the non-aqueous solution in the hollow tube.

Horwood, Corie

Reactive CO 2 capture via controlled amine speciation in non-aqueous electrolytes

Current efforts to integrate CO 2 capture and electrochemical conversion (reactive capture) are often performed under aqueous conditions, resulting in undesired hydrogen evolution and reliance on precious metal catalysts and pure CO 2 streams. Here, in this study, we explore reactive capture in aprotic media. By shifting the amine–CO 2 adduct speciation to carbamic acid (instead of carbamate) in dimethyl sulfoxide, we increased CO 2 uptake threefold compared with an aqueous medium, suppressing hydrogen evolution and supporting a 78% Faradaic efficiency towards CO over an earth-abundant zinc catalyst. Under simulated high-oxygen-content flue gas (17% CO 2 , 17% O 2 , 66% N 2 ), we also obtained up to 43% CO Faradaic efficiency over multiple capture–conversion cycles. Our findings showcase the confluence of reactant speciation, electrolyte composition and electrocatalyst design in enabling selective and active electrochemical transformations.

Gomes, Reginaldo J. [Univ. of Chicago, IL (United

Nanoengineering of non-aqueous liquid electrolyte solutions for future lithium metal batteries

Research and development of non-aqueous electrolyte solutions are essential for practical advancement towards the production of high-energy lithium metal batteries (LMBs). An ideal LMB electrolyte solution should enable highly efficient, uniform and prolonged lithium metal plating and stripping, preserve the electrodes’ electro(chemo)mechanical properties and ensure compatibility with all cell components. However, despite extensive research efforts, scientists have yet to achieve an electrolyte design that meets these requirements simultaneously. Here, by examining the nanoengineering aspects of various non-aqueous electrolyte solution designs, we elucidate the understanding of the nanoscale physicochemical and electrochemical processes taking place in LMBs, which are mainly governed by the thermodynamic and kinetic properties of the electrolyte system. We also explore emerging research directions and propose an accelerated, iterative framework that integrates nanoengineering principles with machine learning, high-throughput computation and experimentation to facilitate the development of next-generation non-aqueous electrolyte solutions for practical LMBs.

Weintz, Dominik

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

Tunable Stabilization of Cuprous Ions via Kinetic and Thermodynamic Control of Cu Electrodeposition in Non-Aqueous Media

In this work, significant stabilization of Cu + ions is achieved in non-aqueous electrolytes containing TFSI - and Cl - anions with diglyme as solvent. When Cl - is absent, stabilization of Cu + occurs due to the very low stability constant of Cu 2+ in diglyme. However, in the presence of relatively low Cl - concentrations (i.e., equimolar relative to Cu 2+ ), both Cu + and Cu 2+ form extremely stable Cu 2+ / + [Cl - ] complexes resulting in a similar to 1200 mV negative shift of the Cu + /0 redox couple relative to that of more easily reduced Cu + [TFSI - ][Cl - ] complexes. Furthermore, these results suggest that the lower solvation energies and wider electrochemical stability windows of non-aqueous solvents relative to water enable anions to play a much more significant role in guiding complexation behavior-providing new possibilities for (electro)chemical stabilization of reactive intermediates and highlighting the wealth of unexplored opportunities for electrolyte design in non-aqueous systems.

Anion Association

A low-cost, fluorine-free electrolyte for improved sodium batteries

Sodium batteries are an attractive alternative to lithium-ion technologies due to sodium’s lower cost and natural abundance—over 1,000 times greater than lithium, comprising approximately 2.4% of the Earth’s crust. However, most current electrolytes rely on fluorine-containing components, which raise economic and environmental concerns. This study explores fluorine-free, borate-based electrolytes that offer improved cycling stability and significant cost and sustainability benefits. We demonstrate stable sodium metal stripping and plating on aluminum foil, enabling anode-free cell configurations with over 50% capacity retention after 700 cycles. Spectroscopic and electrochemical analyses reveal the effects of solvents and salt composition on solvation, ionic conductivity, and oxidative stability. In full-cell configurations, the fluorine-free electrolyte maintains more than 98% capacity retention after 400 cycles. Furthermore, these findings represent a critical step toward the development of cost-effective, environmentally friendly, and high-performance sodium battery systems suitable for future electrification.

anode-free sodium batteries

Interlayer pillaring influences the octahedral tilting and electrochemical capacity of tungsten oxides

One strategy to tune the electrochemical properties of layered inorganic materials for energy storage and conversion is to introduce molecular organic pillars. We investigated how pillaring tungsten oxides with alkylammonium cations influences their physical and electrochemical properties relative to the non-pillared host. While the presence of alkylammonium increased the interlayer spacing, we found that the electrochemical capacity of the materials decreased in non-aqueous electrolytes. In aqueous acidic electrolytes, replacement of the interlayer alkylammonium pillars with water molecules led to the recovery of the electrochemical capacity. We rationalize these results based on the influence of interlayer pillars on the degree of octahedral tilting within the inorganic tungsten oxide layers. The presence of alkylammonium in the interlayer leads to an increase in octahedral tilting relative to interlayer water. In turn, this leads to an increase in the band gap and corresponding decrease in the electrochemical capacity. Our findings emphasize the correlation between the chemical nature of the interlayer molecular pillars and the electronic structure, which in turn affects the electrochemical capacity.

36 MATERIALS SCIENCE

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

Li + (ionophore) nanoclusters engineered aqueous/non-aqueous biphasic electrolyte solutions for high-potential lithium-based batteries

The use of aqueous/non-aqueous biphasic electrolyte solutions in Li-based battery systems circumvents the limitations of poor reductive stability of aqueous electrolyte solutions, broadening their electrochemical stability window. However, aqueous/non-aqueous electrolytes suffer from biphasic mixing and high impedance when Li ions cross the biphasic interface. Here we propose the use of 12-crown-4 (12C4) and tetraglyme (G4) as lithium ionophores to form Li + (ionophore) nanoclusters in both non-aqueous and aqueous phases to overcome the interface challenges in biphasic electrolytes. The Li + (ionophore) nanoclusters have the H 2 O-excluding inner Li + solvation structure in non-polar 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE), allowing fast charge transport across the biphasic interface without solvent mixing or water shuttling. Further, a tailored electrolyte formulation comprising the lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, 12C4, TTE and H 2 O solvents (labelled LiTFSI-12C4@TTE/H 2 O) demonstrates low impedance (2.7 Ω cm -2 ) at the TTE/H 2 O interface and enabling 2,000 cycles of prelithiated graphite||LiFePO 4 coin cells at 850 mA g -1 with an average Coulombic efficiency of 99.8%. Single-layer 22.5 mAh Li||LiMn 2 O 4 pouch cells using LiTFSI-12C4@TTE/H 2 O electrolyte with G4 delivered a stable discharge capacity of about 1.3 mAh cm -2 for 80 cycles at 0.5 mA cm -2 .

25 ENERGY STORAGE