Radiolysis of Electrolytes in Batteries: A Quick and Efficient Screening Process for the Selection of Electrolyte‐Additive Formulations

Levieux‐Souid, Yanis; Martin, Jean‐Frédéric; Moreau, Philippe; Herlin‐Boime, Nathalie; Caër, Sophie Le

doi:10.1002/smtd.202200712

Cited by 6 publications

(4 citation statements)

References 70 publications

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“…Electrolytes exhibit a significant impact on the catalytic nitrate reduction efficiency. 67 The nitrate reduction onset potential of CuCoAl LDH/Vulcan in phosphate buffer (Figure S13a, green) shares a similar value to that observed in the Na 2 SO 4 solution (Figure S13a, blue: 0 V). Interestingly, the total cathodic current density observed in phosphate buffer is 18 mA cm −2 , which is 5 mA cm −2 less than that recorded in a Na 2 SO 4 solution (23 mA cm −2 ).…”

Section: Stability Of Cucoal Ldh Under Long-term Operating Conditions...supporting

confidence: 59%

“…Next, the effect of the electrolyte on the nitrate reduction performance of CuCoAl LDH/Vulcan is explored (Figure S13). Electrolytes exhibit a significant impact on the catalytic nitrate reduction efficiency . The nitrate reduction onset potential of CuCoAl LDH/Vulcan in phosphate buffer (Figure S13a, green) shares a similar value to that observed in the Na 2 SO 4 solution (Figure S13a, blue: 0 V).…”

Section: Results and Discussionmentioning

confidence: 52%

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Synergy between Cu and Co in a Layered Double Hydroxide Enables Close to 100% Nitrate-to-Ammonia Selectivity

Wang,

Chen,

Tse

2023

J. Am. Chem. Soc.

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Nitrate electroreduction (NO 3 RR) holds promise as an energy-efficient strategy for the removal of toxic nitrate to restore the natural nitrogen cycle and mitigate the adverse impacts caused by overfertilization from suboptimal agricultural practices. However, existing catalysts suffer from limited electrocatalytic activity, poor selectivity, inadequate durability, and low scalability. To address this quadrilemma, in this study, we developed a cost-effective layered double hydroxide (LDH) electrocatalyst with a lamellar structure that presents trimetallic CuCoAl active sites on the nanomaterial surface. This codoping design enabled electrochemical upcycling of nitrate into ammonia exclusively and efficiently with an onset potential at 0 V vs RHE, where the electrocatalytic process is less energy intensive and has a lower carbon footprint than conventional practices. The synergistic interaction among Cu, Co, and Al further afforded a 99.5% Faradic efficiency (FE) and a yield rate of 0.22 mol h −1 g −1 for nitrate-to-ammonia electroreduction, surpassing the performance of state-of-the-art nonprecious metal NO 3 RR electrocatalysts over an extended operation period. To gain insights into the origin of the catalytic performance observed on LDH, control materials were employed to elucidate the roles of Cu and Co. Cu was found to improve the NO 3 RR onset potential despite displaying limited FE for ammonia synthesis, while Co was discovered to suppress the formation of nitrite byproduct though requiring large overpotential. Simulated wastewater containing phosphate and sulfate, which are typically present in industrial effluents, was used to further investigate the effect of electrolytes on NO 3 RR. Intriguingly, the use of phosphate buffer resulted in a superior yield rate and FE for ammonia production while simultaneously inhibiting nitrite byproduct formation compared with the sulfate case. These experimental findings were supported by density functional theory (DFT) calculations, which explored the adsorption strength of nitrate adducts adjacent to coadsorbed electrolytes on the LDH surface. Additionally, the relative free energies of NO 3 RR species were also computed to examine the proton-coupled electron transfer (PCET) mechanism on CuCoAl LDH, shedding light on the potential-dependent step (PDS) and the exclusive selectivity for nitrate-to-ammonia conversion. The CuCoAl LDH developed here offers scalability by eliminating the need for precious metals, rendering this earth-abundant catalyst particularly appealing for sustainable nitrate electrovalorization technology.

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Section: Stability Of Cucoal Ldh Under Long-term Operating Conditions...supporting

confidence: 59%

Section: Results and Discussionmentioning

confidence: 52%

Synergy between Cu and Co in a Layered Double Hydroxide Enables Close to 100% Nitrate-to-Ammonia Selectivity

Wang,

Chen,

Tse

2023

J. Am. Chem. Soc.

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“…Electrolytes exhibit a significant impact on the catalytic nitrate reduction efficiency. 76 The nitrate reduction onset potential of CuCoAl LDH/Vulcan in phosphate buffer (Fig. S8a green) is 0.13 V, which is 130 mV more positive relative to that observed in Na2SO4 solution (Fig.…”

Section: Cucoal Ldhmentioning

confidence: 83%

Selective Electroreduction of Nitrate into Ammonia on CuCoAl Layered Double Hydroxide for Sustainable Resourcification

Wang

Chen

Tse

2023

Preprint

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One-step nitrate electroreduction (NO3RR) is a promising strategy to generate ammonia in a straightforward and environmentally friendly manner. However, most catalysts suffer from limited electrocatalytic activity as well as poor selectivity. In this work, a tunable trimetallic CuCoAl layered double hydroxide (LDH) catalyst was designed to generate ammonia exclusively and efficiently with an onset potential at 0.13 V vs. RHE. The synergy among Cu, Co, and Al bestowed a 99.5 % Faradaic efficiency (FE) for ammonia with a yield rate of 0.22 mol h-1 g-1, rivaling the performance of state-of-the-art non-precious metal NO3RR electrocatalysts. Control materials were employed to elucidate the roles of Cu, Co, and Al toward lowering the overpotential and suppressing the formation of nitrite byproduct. DFT calculations were performed to further investigate the adsorption strength of anionic adducts and electrolytes on LDH surface to unravel the effects of buffer conditions on NO3RR performance. The scalable nature of our earth-abundant catalysts is particularly attractive due to the intrinsic low costs of the raw materials. We envision that this precious-metal-free catalyst can be generally applicable to other resourcification processes to achieve a future sustainable society.

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“…Finally, it is fruitful to compare the capabilities of in situ EPR experiments with those of radiolysis, which is recently acknowledged as an analytical tool for accelerated ageing studies of electrolytes. , The radiolysis experiment is designed to mimic the electrolyte degradation occurring in real electrochemical cells by irradiation of electrolytes with energy sufficiently high to cause excitation and ionization of solvent molecules: M → M * , M •+ , e – . , In a mixture of cyclic and linear carbonates, the solvated electron decays ultrafast by attachment exclusively to an EC molecule, leading to the formation of EC anion radicals . The irradiation-generated ion-radicals undergo a series of reactions leading to the release preferentially of CO 2 and CO. , The in situ EPR experiment enables direct monitoring of anion radicals formed at the primary steps of the electrolyte oxidation due to a strong electron affinity of EC. (It is worth recalling that the microwave irradiation energy used in the EPR experiments permits splitting only the spin states of the paramagnetic species, but not to generate new radicals).…”

Section: In Situ Epr Spectroscopy Of Lp30 Electrolytementioning

confidence: 99%

In Situ Electron Paramagnetic Resonance Monitoring of Predegradation Radical Generation in a Lithium Electrolyte

Kukeva,

Kalapsazova,

Rasheev

et al. 2023

J. Phys. Chem. Lett.

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Herein we present an innovative in situ EPR spectroscopy approach complemented with computational modeling as a methodology for assessing a nonaqueous electrolyte behavior just before its massive degradation. As a proof of concept, we use the conventional lithium electrolyte (1 M LiPF6 in EC/DMC), which is utilized in current lithium-ion batteries. Through in situ EPR, long-lived EC•– associates in amounts of 10–250 ppm were detected in a broad potential window (>2.0 V) prior to the electrolyte oxidation or reduction. The pathways of radical formation are discussed in terms of the imperfection in the electron flow across the electrolyte–electrode interface and of the strong affinity of EC to electron trapping. The radical amount could be amplified markedly (above 1000 ppm) by addition of vinylene carbonate (VC) to the electrolyte, while the added CeO2 has a moderate effect. The proposed in situ EPR methodology could be transferred to other electrolyte solutions to become a universal approach.

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Radiolysis of Electrolytes in Batteries: A Quick and Efficient Screening Process for the Selection of Electrolyte‐Additive Formulations

Cited by 6 publications

References 70 publications

Synergy between Cu and Co in a Layered Double Hydroxide Enables Close to 100% Nitrate-to-Ammonia Selectivity

Synergy between Cu and Co in a Layered Double Hydroxide Enables Close to 100% Nitrate-to-Ammonia Selectivity

Selective Electroreduction of Nitrate into Ammonia on CuCoAl Layered Double Hydroxide for Sustainable Resourcification

In Situ Electron Paramagnetic Resonance Monitoring of Predegradation Radical Generation in a Lithium Electrolyte

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