Elucidating the Oxygen Reduction Reaction Kinetics and the Origins of the Anomalous Tafel Behavior at the Lithium–Oxygen Cell Cathode

Sankarasubramanian, Shrihari; Seo, Jong-Soo; Mizuno, Fuminori; Singh, Nikhilendra; Prakash, Jai

doi:10.1021/acs.jpcc.6b09747

Cited by 30 publications

(44 citation statements)

References 54 publications

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“…The outcome of this competition will determine the reaction route followed by the ORR, with superoxide stabilization in solution resulting in a predominantly solution-based ORR and the lack of such stabilization leading to the surface reaction being dominant. The K + solvation sphere is a 3-body system with cation-anion, cationsolvent, and anion-solvent interactions and a single solvent property is not expected to capture the effects of all these interactions [as seen from the discussion regarding the DN, AN, and solvent reorganization energy in our previous work (7)]. Before addressing the effect of the electrolyte formulation on oxygen and the superoxide ion, the degree of cation and anion solvation and possible cation-anion interactions were spectroscopically examined.…”

Section: Resultsmentioning

confidence: 99%

“…Thus, the oxygen reduction reaction (ORR) is the key to the rapid growth of battery specific energy density required for long-range electric transportation, ever-more energy-intensive electronic devices, and long-duration (10 to 100 h per cycle) energy storage (1)(2)(3). Since the demonstration of the secondary Li-O 2 cell by Abraham and Jiang (4), the ORR in nonaqueous electrolytes has been the subject of sustained interest (5)(6)(7). Unfortunately, Li-O 2 batteries suffer due to the high-energy barrier to the oxygen evolution reaction (OER) (1,8), parasitic side reactions (9), Li dendrite growth (10), and unstable electrolytes (11)(12)(13)(14).…”

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confidence: 99%

“…This study extends the fundamental kinetic understanding of the ORR in a K-O 2 cell achieved in the work of Sankarasubramanian and Ramani (5) and examines the influence of the electrolyte formulation on the ORR in K-O 2 cells. The influence of the solvent on the solubility and the solvation of the salt has been previously studied in other alkali metal-oxygen cells in terms of both the Pearson hard-soft acid-base (HSAB) theory (42) and in terms of the solvent reorganization energy ðλÞ from Marcus-Hush theory (7). Furthermore, it has been shown that the ORR in Li-O 2 and Na-O 2 cells, which are analogous to K-O 2 cells, displays a strong dependence on the electrolyte solvent (42)(43)(44)(45)(46)(47), salt (48,49), and additives present (22,(50)(51)(52)(53).…”

mentioning

confidence: 99%

“…This electrochemical Thiele modulus involves a potential dependent k (unlike the constant k in the typical isothermal reaction engineering case). The inherent limitation of the DN and AN of a solvent or the salt to describe the solvation structure in an electrolyte can be overcome by the use of the solvent reorganization energy, which is the amount of energy required to change the solvation shell of the reactants to that of the product during an electrochemical reaction, and which plays a prominent part in the Marcus-Hush kinetic formulation (7,59,67). Thus, it encompasses both the ease of solvation of a given species and the ease of oxidizing or reducing it (λ=F may be used to calculate the overpotential required to rearrange or break the solvation shell of a given reactant).…”

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confidence: 99%

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Tuning anion solvation energetics enhances potassium–oxygen battery performance

Sankarasubramanian

Kahky

Ramani

2019

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

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The oxygen reduction reaction (ORR) is a critical reaction in secondary batteries based on alkali metal chemistries. The nonaqueous electrolyte mediates ion and oxygen transport and determines the heterogeneous charge transfer rates by controlling the nature and degree of solvation. This study shows that the solvent reorganization energy (λ) correlates well with the oxygen diffusion coefficient (DO2) and with the ORR rate constant (k) in nonaqueous Li–, Na–, and K–O2 cells, thereby elucidating the impact of variations in the solvation shell on the ORR. Increasing cation size (from Li+ to K+) doubled k/λ, indicating an increased sensitivity of k to the choice of anion, while variations in DO2were minimal over this cation size range. At the level of a symmetric K–O2 cell, both the formation of solvent-separated ion pairs [K+–(DMSO)n–ClO4− + (DMSO)m–ClO4−] and the anions being unsolvated (in case of PF6−) lowered ORR activation barriers with a 200-mV lower overpotential for the PF6− and ClO4− electrolytes compared with OTf− and TFSI− electrolytes with partial anion solvation [predominantly K+–(DMSO)n–OTf−]. Balancing transport and kinetic requirements, KPF6 in DMSO is identified as a promising electrolyte for K–O2 batteries.

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Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Tuning anion solvation energetics enhances potassium–oxygen battery performance

Sankarasubramanian

Kahky

Ramani

2019

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

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“…Находясь в растворителях и имея в них положительное сродство к электрону, молекулы кислорода способны захватывать электроны катодных электродов. Это снижает электрическую емкость, например, литиевых аккумуляторов и создает АФК О 2 -, которые вступают во взаимодействие с органическими растворителями и разрушают электрические цепи переноса катионов лития на анодный электрод внутри аккумуляторов [4].…”

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Computer Simulation of the O2- Superoxide Ion Stability in a Continuous Dielectric Medium

et al. 2020

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In this paper, computer modeling is carried out, and stability parameters (total energy, binding energy, ionization and electron affinity, vibrational frequencies) at the ground states of the O2 (X 3Zg-) molecule and the superoxide ion O2- (X 2Пg) in dielectric media are calculated. Chemical particles have been placed in the topological cavity of the continuum medium. The CPCM model takes into account cavitation energy, electrostatic and dispersion interactions with a continuous polarized solvent medium. Calculations are performed using the algorithms of the ORCA package by the method of the hybrid density functional B3LYP in the basic set 6-31+G (d). The calculated data for effective media with a dielectric constant of vacuum, benzene, and water are obtained. It is shown that an increase in the dielectric constant of the solvent significantly increases the stability of the O2- superoxide ion with respect to oxidation and transition to an inactivated state of an oxygen molecule with a calculated electron affinity of 0.495 eV, 2.723 eV, 3.803 eV for vacuum, benzene, and water, respectively.

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An Enhanced Extend Interface via the π–π Interaction to Achieve the Soluble Light‐Assisted Lithium–Oxygen Batteries

Wang,

Song,

Wang

et al. 2024

Adv Funct Materials

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The light‐assisted strategy is considered as an effective way to reduce the overpotential of lithium‐oxygen (Li─O2) batteries, however, the generated solid discharge products are prone to cover active sites of the solid‐state photocatalyst, causing the premature death of the cell. Herein, for the first time, the feasibility of soluble photocatalysts in Li─O2 battery system using Iron (II) Phthalocyanine (FePc) is verified. A micro reaction channel is constructed between the sp2‐carbon cathode and the soluble photocatalyst‐phthalein iron through π–π interaction, which can effectively increase the three‐phase reaction interface, facilitating the rapid separation and the transportation of photogenerated electrons and holes, thus improving the photocatalytic efficiency and the reaction kinetics of Li─O2 battery. Moreover, the FePc soluble photocatalysts induced the dual growth modes of surface growth and solution‐mediated growth pathways for the discharge products lead to an additional discharge capacity in the Li─O2 battery. Accordingly, the battery exhibits a lower overpotential of 0.33 V between discharge and charge plateaus at a current density of 0.01 mA cm−2, displaying the excellent cyclic stability (remaining a round‐trip efficiency of 81.1% after 130 cycles). The novel strategy provides new approaches for the construction of the light‐assisted Li─O2 batteries with reduced overpotential and boosted energy efficiency.

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Elucidating the Oxygen Reduction Reaction Kinetics and the Origins of the Anomalous Tafel Behavior at the Lithium–Oxygen Cell Cathode

Cited by 30 publications

References 54 publications

Tuning anion solvation energetics enhances potassium–oxygen battery performance

Tuning anion solvation energetics enhances potassium–oxygen battery performance

Computer Simulation of the O2- Superoxide Ion Stability in a Continuous Dielectric Medium

An Enhanced Extend Interface via the π–π Interaction to Achieve the Soluble Light‐Assisted Lithium–Oxygen Batteries

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