Aqueous and nonaqueous lithium-air batteries enabled by water-stable lithium metal electrodes

Visco, Steven J.; Nimon, Vitaliy; Petrov, A. V.; Pridatko, K. I.; Goncharenko, Nikolay; Nimon, Eugene; Jonghe, Lutgard De; Volfkovich, Yury M.; Bograchev, D. A.

doi:10.1007/s10008-014-2427-x

Cited by 39 publications

(58 citation statements)

References 30 publications

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“…We note that because the solubility is an exponential function of solvation energies, small errors in solvation energy calculation will lead to a significant difference in the calculated absolute solubility. Our calculations showing that Li 2 O 2 is very insoluble in DME and other solvents is consistent with some studies 19,20 and in disagreement with others [21][22][23][24] which are many orders of magnitudes larger (details on these experimental measurements were discussed earlier). For example, the solubility of 10 [21][22][23][24] could be for several reasons.…”

Section: Resultssupporting

confidence: 91%

“…Our calculations showing that Li 2 O 2 is very insoluble in DME and other solvents is consistent with some studies 19,20 and in disagreement with others [21][22][23][24] which are many orders of magnitudes larger (details on these experimental measurements were discussed earlier). For example, the solubility of 10 [21][22][23][24] could be for several reasons. One possibility is that since Li 2 O 2 is known to react with H 2 O, trace amounts of water contamination in solution might result in erroneous solubility measurement and in one case the solubility closely matched the ppm of water reported in the solvent.…”

Section: Resultssupporting

confidence: 91%

“…One possibility is that since Li 2 O 2 is known to react with H 2 O, trace amounts of water contamination in solution might result in erroneous solubility measurement and in one case the solubility closely matched the ppm of water reported in the solvent. 22 Another possibility is that solubility measurements may depend on particle size or surface effects that increase solubility.…”

Section: Resultsmentioning

confidence: 99%

“…Lodge et al 19 reported a solubility product constant of Li 2 22 1 mM in acetronitrile/propylene carbonate mixture 23 and 0.02 mM in propylene carbonate and dimethyl carbonate mixture. 24 The reason for the wide range of values for the solubility is unclear.…”

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confidence: 99%

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Computational Studies of Solubilities of LiO₂and Li₂O₂in Aprotic Solvents

Cheng¹,

Redfern²,

Lau³

et al. 2017

J. Electrochem. Soc.

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Knowledge of the solubilities of Li 2 O 2 and LiO 2 in aprotic solvents is important for insight into the discharge and charge processes of Li-O 2 batteries, but these quantities are not well known. In this contribution, the solvation free energies of molecular LiO 2 and Li 2 O 2 in various organic solvents were calculated using various explicit and implicit solvent models, as well as ab initio molecular dynamics (AIMD) methods. The solvation energies from these calculations along with calculated lattice energies of Li 2 O 2 and LiO 2 were used to determine the solubility of bulk LiO 2 and Li 2 O 2 . The computed solubility of LiO 2 (1.8 × 10 −2 M) is about 15 orders higher than that of Li 2 O 2 (2.0 × 10 −17 M) due to a much less negative lattice energy of bulk LiO 2 compared to that of Li 2 O 2 . The difference in solubilities between LiO 2 and Li 2 O 2 likely will affect the nucleation and growth mechanisms and resulting morphologies of the products formed during battery discharge, influencing the performance of the battery cell. Lithium-O 2 battery technology has received much research interest due to its high theoretical gravimetric energy density compared to conventional Li-ion batteries.1 The system uses oxidation of lithium at the anode and reduction of oxygen at the cathode to induce a current flow. Depending on the reaction kinetics of different discharge mechanisms, the discharge products are generally composed of Li 2 O 2 with a low solubility and in some cases different ratios of LiO 2 and Li 2 O 2 .2-6 Much of research focus has been on the cathode. One of the challenges of Li-O 2 batteries is the incomplete utilization of the active materials due to the insulating nature of the discharge products and the clogging the porous carbon cathode. The formation of these products may involve a nucleation and growth mechanism from the solution phase.2,7-13 Nazar reported a Li 2 O 2 formation mechanism by disproportionation reaction of a limited amount of LiO 2 in solution.2 A through-solution mechanism was also proposed involving heterogeneous nucleation from a supersaturated solution of LiO 2 . 10There is other evidence that LiO 2 is soluble in the electrolyte prior to deposition on the surface based on a quartz microbalance study.14 Results from several research groups suggest that the composition and morphology of the discharge products have a significant effect on charging overpotential and rechargeability of the Li-O 2 battery. 10,15,16 Therefore, understanding the chemistry and growth mechanism of discharge products in the cell is crucial for improving Li-O 2 battery. The study and modeling of nucleation and crystal growth requires knowledge of bulk solubility. 17,18 However, there are limited experimental solubility measurements reported in the literature on discharge products LiO 2 and Li 2 O 2 . Solubility also highly depends on the size and morphologies of the solid as well as impurities so the values will depend on the experimental conditions. 24 The reason for the wide range of values for the s...

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Section: Resultssupporting

confidence: 91%

Section: Resultssupporting

confidence: 91%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

See 2 more Smart Citations

Computational Studies of Solubilities of LiO₂and Li₂O₂in Aprotic Solvents

Cheng¹,

Redfern²,

Lau³

et al. 2017

J. Electrochem. Soc.

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“…uniform layers can serve as an artificial SEI layer and have received some research attention lately. [88,89] Thei ssues connected to the reactivity of carbon surfaces may be mitigated by coating the cathode with passivation layers. But such an approach also makes it difficult to take advantage of the good ORR activity of carbon, which may increase the discharge overpotentials.T os olve the problem, researchers have started looking into the possibility of promoting oneelectron reaction pathways by choosing appropriate electrolytes.A dditionally,r esearchers have studied the possibilities of controlling the reaction pathways by altering the carbon surfaces and morphologies.…”

Section: Discussionmentioning

confidence: 99%

Why Do Lithium–Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect

et al. 2016

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Lithium/Sulfide All‐Solid‐State Batteries using Sulfide Electrolytes

et al. 2020

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All‐solid‐state lithium batteries (ASSLBs) are considered as the next generation electrochemical energy storage devices because of their high safety and energy density, simple packaging, and wide operable temperature range. The critical component in ASSLBs is the solid‐state electrolyte. Among all solid‐state electrolytes, the sulfide electrolytes have the highest ionic conductivity and favorable interface compatibility with sulfur‐based cathodes. The ionic conductivity of sulfide electrolytes is comparable with or even higher than that of the commercial organic liquid electrolytes. However, several critical challenges for sulfide electrolytes still remain to be solved, including their narrow electrochemical stability window, the unstable interface between the electrolyte and the electrodes, as well as lithium dendrite formation in the electrolytes. Herein, the emerging sulfide electrolytes and preparation methods are reviewed. In particular, the required properties of the sulfide electrolytes, such as the electrochemical stabilities of the electrolytes and the compatible electrode/electrolyte interfaces are highlighted. The opportunities for sulfide‐based ASSLBs are also discussed.

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Aqueous and nonaqueous lithium-air batteries enabled by water-stable lithium metal electrodes

Cited by 39 publications

References 30 publications

Computational Studies of Solubilities of LiO₂and Li₂O₂in Aprotic Solvents

Computational Studies of Solubilities of LiO₂and Li₂O₂in Aprotic Solvents

Why Do Lithium–Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect

Lithium/Sulfide All‐Solid‐State Batteries using Sulfide Electrolytes

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Aqueous and nonaqueous lithium-air batteries enabled by water-stable lithium metal electrodes

Cited by 39 publications

References 30 publications

Computational Studies of Solubilities of LiO2and Li2O2in Aprotic Solvents

Computational Studies of Solubilities of LiO2and Li2O2in Aprotic Solvents

Why Do Lithium–Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect

Lithium/Sulfide All‐Solid‐State Batteries using Sulfide Electrolytes

Contact Info

Product

Resources

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Computational Studies of Solubilities of LiO₂and Li₂O₂in Aprotic Solvents

Computational Studies of Solubilities of LiO₂and Li₂O₂in Aprotic Solvents