Cathode candidates for zinc-based thermal-electrochemical energy storage

Holubowitch, Nicolas E.; Manek, Stephen; Landon, James; Lippert, Cameron A.; Odom, Susan A.; Liu, Kunlei

doi:10.1002/er.3385

Cited by 7 publications

(5 citation statements)

References 29 publications

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“…The above analysis could also explain the >100% coulombic efficiencies observed in the first cycles, where Bi(l) may irreversibly accept small amounts of reduced Zn, although elemental analysis did not indicate the presence of Zn in the Bi electrode. Also possible is the dissolution of electrodes into the molten salt electrolyte as solvated, reduced metal; however, in this work and previous work we observed negligible self‐discharge, energy‐dispersive X‐ray (EDX), or differential scanning calorimetry (DSC) data that would suggest significant metal dissolution had occurred . Insoluble species may be deposited as a thin solid‐electrolyte interphase (SEI) at one or both of the electrodes from a small uptake of ambient O 2 or H 2 O during testing (e.g., in the form of ZnO or oxychlorides).…”

Section: Resultsmentioning

confidence: 52%

“…Thus, Sn ( ρ m = 7.0 g cm −3 ) was selected as a compatible host anode metal . Ultimately, Bi was selected as a cathode candidate because it has the largest reduction potential relative to Zn and the largest predicted power density as a cathode in our previous studies . These results led us to develop the all‐molten Sn(Zn)|ZnCl 2 :KCl|Bi cell.…”

Section: Resultsmentioning

confidence: 99%

“…The temperature of the cell was then lowered to operating temperature (typically 320 °C); the transparent liquid electrolyte covered the molten metal electrodes by about 1 cm. Before cycling experiments, contacts were made to the molten metal electrodes using graphite rods, which were observed not to interfere with the battery's electrochemistry, and the cell was covered with an insulating ceramic fiber sheet. No visible changes in electrolyte opacity were observed after several days of experiments, indicating minimal insoluble oxide or oxychloride formation.…”

Section: Methodsmentioning

confidence: 99%

“…A challenge with Zn is its tendency to form passivating oxide films, but nonaqueous, high temperature systems based on alloys may solve this issue. Our motivation stemmed from prior work in which we evaluated solid Zn as an anode in combination with various solid and molten cathode candidates, using the eutectic ZnCl 2 :KCl as a molten salt electrolyte . In experiments simulating primary cells, we observed short circuit currents and theoretical power outputs which were strongly dependent on the phase of the cathode material: molten cathodes (Sn, Bi, and Pb) yielded high and sustained currents.…”

Section: Introductionmentioning

confidence: 99%

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Molten Zinc Alloys for Lower Temperature, Lower Cost Liquid Metal Batteries

Holubowitch

Manek

Landon

et al. 2016

Adv Materials Technologies

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(1 of 9) 1600035 wileyonlinelibrary.com grid storage. To date, much research in EES has focused on batteries with lithium as a charge carrier, spurred by success in portable electronics, but high costs, short lifetimes, and safety issues make lithium technology less than ideal for grid storage. [4][5][6][7] The chemistry of all-vanadium redox fl ow batteries has yielded promising cycle lifetimes, but this technology is hindered by the high cost of vanadium and low energy densities and round-trip efficiencies. [8][9][10] For EES technologies to be practical for grid storage, systems must utilize low-cost, abundant, and safe materials.Liquid metal batteries (LMBs), which contain molten metal electrodes and molten salt electrolytes, have recently re-emerged as candidates for grid storage technologies. [ 11,12 ] These batteries, which contain socalled "structureless" electrodes, are not susceptible to mechanical degradation inherent with intercalation-type electrochemistry. Until now LMB technologies have featured a design in which the immiscible molten materials naturally stratify into three layers, where the density of the electrolyte lies between that of the two electrodes. While this design simplifi es battery fabrication, the relative density requirement (i) limits materials choices, precluding the use of many low-cost materials, (ii) necessitates exceedingly high operating temperatures, and/or (iii) compromises on safety due to material reactivity. [ 13,14 ] Recently reported LMBs contain highly reactive metals such as Ca, Mg, or Li and operate at high temperatures (450-700 °C). Furthermore, the stratifi ed LMB design is susceptible to electrode dissolution and magnetohydrodynamic instabilities at high current densities, which could lead to cell shorting and thermal runaway. [ 11 ] Other recent examples of batteries containing a liquid metal electrode include Na-NiCl 2 batteries and Na-S batteries; these electrodes are separated by a ceramic membrane and do not have the strict requirements of relative densities and immiscibility and can reach lower operating temperatures. However, the performance of these batteries is limited by the inclusion of nonconducting materials in the electrode (NiCl 2 or S), and the batteries still pose dangers because they contain corrosive liquids and brittle membranes. [15][16][17] In the present work, we sought to address the shortcomings of the above technologies while keeping material and energy costs low by creating a zinc-based LMB. Zinc (Zn), an inexpensive multivalent energy carrier, has a high theoretical energy density of 820 mAh g −1 , and, in an all-molten cell design, Molten Zinc Alloys for Lower

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Section: Resultsmentioning

confidence: 52%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Molten Zinc Alloys for Lower Temperature, Lower Cost Liquid Metal Batteries

Holubowitch

Manek

Landon

et al. 2016

Adv Materials Technologies

Self Cite

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“…Fernández‐Olmo et al concluded that for the semiconductor manufacturing, it is required to use high‐purity chemical products, to avoid short circuits as a consequence of some deformation occurring in the electronic wafers, resulting in performance loss. In addition, it has been determined that the impurities contained in the materials used in the manufacturing process of the batteries can affect their performance …”

Section: Introductionmentioning

confidence: 99%

Purification of brines by chemical precipitation and ion-exchange processes for obtaining battery-grade lithium compounds

et al. 2018

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Lithium salts are very important in the production of lithium batteries since they are used as precursors for the fabrication of cathode materials that require very low level of impurities (battery grade). Usually, the lithium extraction process from brine first yields lithium carbonate, which is then used as raw material for the production of other lithium compounds. However, it implies an increase in investment costs, considering more equipment and process stages. To remove the impurities and produce battery-grade lithium compounds directly from brines, a laboratory-scale process was developed using the methods of ion exchange and chemical precipitation. Thus, impurity-free brine ready to be used in an industrial membrane electrolysis process is obtained.Different sequences and operating conditions were investigated for the purification of lithium-concentrated brines, removing the main impurities of the natural brines: calcium, magnesium, and sulfate. For the characterization of solutions, crystals, and ion-exchange resins, atomic absorption spectrophotometry, scanning electron microscopy, and X-ray scattering spectroscopy were used. The results indicate that during the chemical precipitation process, lithium-concentrated brine reacted with some additives (precipitating agents) at different stages in the batch reactors. Subsequently, the pulp obtained was sedimented and filtered, eliminating or reducing the impurities of the lithium brine. Thus, the most efficient precipitation sequence was evaluated as a function of the removal percentage of the species. The removal efficiencies obtained for Ca +2 , Mg +2 , and SO 4 −2 were of 98.93%, 99.93%, and 97.14%, respectively.Thereafter, the use of the ion-exchange resins reduced the concentration of Ca +2 and Mg +2 to the values below 1 ppm. The combined use of both processes provided promising results that could be applied in the industry.

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Competing forces in liquid metal electrodes and batteries

Ashour

Kelley

Salas

et al. 2018

Journal of Power Sources

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Liquid metal batteries are proposed for low-cost grid scale energy storage. During their operation, solid intermetallic phases often form in the cathode and are known to limit the capacity of the cell. Fluid flow in the liquid electrodes can enhance mass transfer and reduce the formation of localized intermetallics, and fluid flow can be promoted by careful choice of the locations and topology of a battery's electrical connections. In this context we study four phenomena that drive flow: Rayleigh-B\'enard convection, internally heated convection, electro-vortex flow, and swirl flow, in both experiment and simulation. In experiments, we use ultrasound Doppler velocimetry (UDV) to measure the flow in a eutectic PbBi electrode at 160{\deg}C and subject to all four phenomena. In numerical simulations, we isolate the phenomena and simulate each separately using OpenFOAM. Comparing simulated velocities to experiments via a UDV beam model, we find that all four phenomena can enhance mass transfer in LMBs. We explain the flow direction, describe how the phenomena interact, and propose dimensionless numbers for estimating their mutual relevance. A brief discussion of electrical connections summarizes the engineering implications of our work

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Cathode candidates for zinc-based thermal-electrochemical energy storage

Cited by 7 publications

References 29 publications

Molten Zinc Alloys for Lower Temperature, Lower Cost Liquid Metal Batteries

Molten Zinc Alloys for Lower Temperature, Lower Cost Liquid Metal Batteries

Purification of brines by chemical precipitation and ion-exchange processes for obtaining battery-grade lithium compounds

Competing forces in liquid metal electrodes and batteries

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