Lithium Nitrate As Regenerable SEI Stabilizing Agent for Rechargeable Li/O<sub>2</sub> Batteries

Uddin, Jasim; Bryantsev, Vyacheslav S.; Giordani, Vincent; Walker, Wesley; Chase, Gregory V.; Addison, Dan

doi:10.1021/jz402025n

Cited by 109 publications

(123 citation statements)

References 18 publications

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“…This result is in good agreement with those for LiNO 3 -based electrolytes, in which the NO 3 − anion acts as a mild oxidant for the Li metal NE to form a stable oxide film. [29][30][31] Thus, the Li dissolution/deposition reaction rate depends on the formation of an Li oxide layer, containing Li 2 CO 3 , on the Li metal NEs. This suggests that control of the oxidation state of the Li metal NE surface is key to enhance and maintain good LAB performance.…”

Section: Resultsmentioning

confidence: 99%

Effects of Li Salt Anions and O₂Gas on Li Dissolution/Deposition Behavior at Li Metal Negative Electrode for Non-Aqueous Li-Air Batteries

Saito

Fujinami

Yamada

et al. 2017

J. Electrochem. Soc.

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To clarify the relationship between Li + transport rate in glyme-based electrolytes and Li deposition/dissolution behavior at Li metal negative electrode (NE) in Li-air batteries (LAB) systems, 1.0 M tetraglyme (G4) electrolytes were prepared containing a Li salt of LiSO 3 CF 3 , LiN(SO 2 CF 3 ) 2 , or LiN(SO 2 F) 2 . Two aspects of Li + transfer between the two phases, i.e., G4 electrolyte | Li metal NE, were evaluated, namely i) Li + supplying rate and ii) Li + charge transfer rate through solid electrolyte interphase (SEI) films. The former was investigated by self-diffusion coefficients D of Li + , anions, and G4 solvent together with ionic conductivity σ, viscosity, density, and apparent dissociation degree α app of the Li salts estimated by the Nernst-Einstein equation. The latter was evaluated with Li | Li symmetric and LAB (Li | O 2 ) cells containing the electrolytes. The Li deposition/dissolution reaction basically depended on the Li + supplying rate in the Li | Li cell; however Li dendrites were formed. Conversely, the LAB cell performance was controlled by Li oxide layers formed on the NE, resulting in similar discharge/charge properties without Li dendrites. The effects of surface-oxidation was also confirmed with Li | Li cells containing O 2 gas, where both SEI and charge transfer resistances were In recent years, rechargeable non-aqueous Li-air batteries (LABs) have received increasing attention as large-scale energy storage devices for long-range electric vehicles (EVs), because of their high energy density, more than five times greater than that of conventional Liion batteries (LIBs).1-4 However, some problems need to be addressed to enable the realization of this technology, including choking of the air electrode by Li 2 O 2 generated during discharging and the high overpotential required by Li 2 O 2 oxidation reaction during charging. These factors lead to oxidative deterioration of the electrolytes and the air electrode, which consists of porous carbon materials. At the Li metal negative electrode (NE), Li dendrite growth during discharge/charge cycles also poses serious safety problems. 15 has been suggested as a way of avoiding the short circuiting of cells caused by Li dendrite growth. However, the additives commonly used to control the solid electrolyte interphase (SEI) film do not effectively work in LAB systems. In these systems the Li dissolution/deposition reaction is repeated many times and O 2 gas is fed in from the air electrode, resulting in destabilization of the SEI films. Furthermore, carbonatetype electrolytes are decomposed by O 2 − radicals generated at the air electrode during the discharge process. Recently, ether-based electrolytes, based on 1,2 dimethoxyethane (DME or G1), diglyme (G2), triglyme (G3), or tetraglyme (G4) as a solvent, have been widely investigated for non-aqueous LAB systems. 16 These ethers have high oxygen solubility and relatively low electric constants, resulting in lower reactivity toward O 2 − radicals than that of carbonate-based electrolytes.17 H...

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Section: Resultsmentioning

confidence: 99%

Effects of Li Salt Anions and O₂Gas on Li Dissolution/Deposition Behavior at Li Metal Negative Electrode for Non-Aqueous Li-Air Batteries

Saito

Fujinami

Yamada

et al. 2017

J. Electrochem. Soc.

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“…Furthermore, using quantitative measures of battery rechargeability, high-DN solvents, such as DMSO and N-methyl pyrrolidone, have been observed to be less stable than low-DN solvents, such as acetonitrile and DME (14). Recently, Khetan et al used a thermodynamic analysis to show that an organic solvent's ability to induce the solution mechanism is anticorrelated with its stability toward nucleophilic attack (15 (16,17). We found that electrolytes containing a high concentration of NO 3 − exhibited higher donicity, as verified using 7 Li NMR, and provided an increase in battery capacity greater than fourfold compared with a battery using exclusively TFSI − as the electrolyte anion, while not decreasing battery rechargeability, as measured using quantitative oxygen consumption and evolution.…”

Section: Significancementioning

confidence: 99%

Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li–O ₂ battery capacity

Burke

Pande

Khetan

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

319

344

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Among the "beyond Li-ion" battery chemistries, nonaqueous Li-O 2 batteries have the highest theoretical specific energy and, as a result, have attracted significant research attention over the past decade. A critical scientific challenge facing nonaqueous Li-O 2 batteries is the electronically insulating nature of the primary discharge product, lithium peroxide, which passivates the battery cathode as it is formed, leading to low ultimate cell capacities. Recently, strategies to enhance solubility to circumvent this issue have been reported, but rely upon electrolyte formulations that further decrease the overall electrochemical stability of the system, thereby deleteriously affecting battery rechargeability. In this study, we report that a significant enhancement (greater than fourfold) in Li-O 2 cell capacity is possible by appropriately selecting the salt anion in the electrolyte solution. Using 7 Li NMR and modeling, we confirm that this improvement is a result of enhanced Li + stability in solution, which, in turn, induces solubility of the intermediate to Li 2 O 2 formation. Using this strategy, the challenging task of identifying an electrolyte solvent that possesses the anticorrelated properties of high intermediate solubility and solvent stability is alleviated, potentially providing a pathway to develop an electrolyte that affords both high capacity and rechargeability. We believe the model and strategy presented here will be generally useful to enhance Coulombic efficiency in many electrochemical systems (e.g., Li-S batteries) where improving intermediate stability in solution could induce desired mechanisms of product formation.donor number | solubility | lithium nitrate | NMR | Li-air battery T he lithium-oxygen (Li-O 2 ) battery has garnered significant research interest in the past 10 y due to its high theoretical specific energy compared with current state-of-the-art lithiumion (Li-ion) batteries (1, 2). Consisting of a lithium anode and an oxygen cathode, the nonaqueous Li-O 2 battery operates via the electrochemical formation and decomposition of lithium peroxide (Li 2 O 2 ). The ideal overall reversible cell reaction is thereforeOne challenge preventing the realization of a modest fraction of the Li-O 2 battery's high theoretical specific energy is that the discharge product, Li 2 O 2 , which is generally insoluble in aprotic organic electrolytes, is an insulator (3-5). As Li 2 O 2 is conformally deposited on the cathode's carbon support during discharge, it electronically passivates the cathode, resulting in practical capacities much smaller than theoretically attainable (6). Recently, two reports described the engineering of electrolytes to circumvent this passivation and improve Li-O 2 battery discharge capacity. Aetukuri et al. suggested that adding ppm quantities of water to a 1,2-dimethoxyethane (DME)-based electrolyte increases the solubility of intermediates during Li 2 O 2 formation (7). This increased solubility allows a reduced oxygen species shuttling mechanism that promotes deposi...

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“…There are many studies that use LiNO 3 in conjunction with other RMs to further improve battery performance . However, LiNO 3 only works in the presence of Li metal because LiNO 2 would be spontaneously oxidized in the presence of O 2 to LiNO 3 and it is not stay stable as LiNO 2 in the cell …”

Section: Redox Mediators For Chargementioning

confidence: 99%

“…[36] However,LiNO 3 only works in the presence of Li metal because LiNO 2 would be spontaneously oxidized in the presence of O 2 to LiNO 3 and it is not stay stable as LiNO 2 in the cell. [37]…”

Section: Other Rm Charmentioning

confidence: 99%

Promoting Li–O₂ Batteries With Redox Mediators

Shen

Zhang

et al. 2019

ChemSusChem

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Li–O2 batteries have a high theoretical specific energy, 3500 Wh kg−1; however, its practical capacity is far below this value and limited by the passivation with the insulating discharge product Li2O2. The nonconductive nature of Li2O2 also impedes the charging process, leading to a low coulombic efficiency and high overpotential on charge even at a moderate rate. To address these challenges, redox mediators could be used both during discharge and charge to transfer electrons between O2/electrode surface or Li2O2/electrode surface to overcome the passivation of Li2O2, which would facilitate the discharge and charge process. The capacity and current density were significantly improved using the redox mediators, thus representing a promising strategy to achieve a high energy density for Li–O2 batteries.

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Lithium Nitrate As Regenerable SEI Stabilizing Agent for Rechargeable Li/O₂ Batteries

Cited by 109 publications

References 18 publications

Effects of Li Salt Anions and O₂Gas on Li Dissolution/Deposition Behavior at Li Metal Negative Electrode for Non-Aqueous Li-Air Batteries

Effects of Li Salt Anions and O₂Gas on Li Dissolution/Deposition Behavior at Li Metal Negative Electrode for Non-Aqueous Li-Air Batteries

Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li–O ₂ battery capacity

Promoting Li–O₂ Batteries With Redox Mediators

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Lithium Nitrate As Regenerable SEI Stabilizing Agent for Rechargeable Li/O2 Batteries

Cited by 109 publications

References 18 publications

Effects of Li Salt Anions and O2Gas on Li Dissolution/Deposition Behavior at Li Metal Negative Electrode for Non-Aqueous Li-Air Batteries

Effects of Li Salt Anions and O2Gas on Li Dissolution/Deposition Behavior at Li Metal Negative Electrode for Non-Aqueous Li-Air Batteries

Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li–O 2 battery capacity

Promoting Li–O2 Batteries With Redox Mediators

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Product

Resources

About

Lithium Nitrate As Regenerable SEI Stabilizing Agent for Rechargeable Li/O₂ Batteries

Effects of Li Salt Anions and O₂Gas on Li Dissolution/Deposition Behavior at Li Metal Negative Electrode for Non-Aqueous Li-Air Batteries

Effects of Li Salt Anions and O₂Gas on Li Dissolution/Deposition Behavior at Li Metal Negative Electrode for Non-Aqueous Li-Air Batteries

Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li–O ₂ battery capacity

Promoting Li–O₂ Batteries With Redox Mediators