On the incompatibility of lithium–O<sub>2</sub> battery technology with CO<sub>2</sub>

Zhang, Shiyu; Nava, Matthew; Chow, Gary K; López, Nazario; Wu, Gang; Britt, David; Nocera, Daniel G.; Cummins, Christopher C.

doi:10.1039/c7sc01230f

Cited by 33 publications

(53 citation statements)

References 39 publications

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“…[51][52][53] Oxygen radicals that form in Li-O2 batteries are, on the other hand, highly reactive, and EPR studies have employed spin traps, which are reagents added to the electrolyte solution that form stable EPR active adducts with radical oxygen species, to elucidate the mechanism of Obased reactions. 54,55 Magnetometry studies of battery electrodes and devices. For electrode materials exhibiting Curie-Weiss behavior, the bulk magnetic susceptibility c and Weiss constant qCW can provide insights into the local structure and the presence of defects 7,56 .…”

Section: Epr Studies Of Beyond Li-ion Batteries Epr Has Been Used To Investigate Li-s and Li-o2mentioning

confidence: 99%

Rechargeable Batteries from the Perspective of the Electron Spin

Nguyen

Clément

2020

ACS Energy Lett.

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Rechargeable batteries generate current through the transfer of electrons between paramagnetic and/or metallic electrode materials. Electron spin probes, such as electron paramagnetic resonance (EPR) and magnetometry, can therefore provide detailed insight into the underlying energy storage mechanisms. These techniques have been applied ex situ, and more recently operando, to both intercalation-and conversion-type batteries. After briefly reviewing the principles of EPR and magnetometry, this perspective provides a critical discussion of recent studies that leverage these tools to understand the local structure, defect chemistry and charge/discharge and failure mechanisms of rechargeable batteries. Challenges in data collection and interpretation are addressed and strategies to facilitate EPR spectral assignment and expand the scope of EPR and magnetometry studies of battery systems are suggested.

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Section: Epr Studies Of Beyond Li-ion Batteries Epr Has Been Used To Investigate Li-s and Li-o2mentioning

confidence: 99%

Rechargeable Batteries from the Perspective of the Electron Spin

Nguyen

Clément

2020

ACS Energy Lett.

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“…Li-O2 batteries could surpass current Li-ion batteries in energy, sustainability, and cost (4). However, practically realizing high reversible capacities faces the challenges of forming/decomposing large amounts of Li2O2 while suppressing parasitic reactions (5,(7)(8)(9)(10)(11). These challenges are interrelated and require understanding the interplay between physical chemistry and structural evolution at the nanoscale (2,(12)(13)(14)(15)(16).…”

Section: Main Text Introductionmentioning

confidence: 99%

In situ small-angle X-ray scattering reveals solution phase discharge of Li–O ₂ batteries with weakly solvating electrolytes

Prehal

Samojlov

Nachtnebel

et al. 2021

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

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Electrodepositing insulating lithium peroxide (Li2O2) is the key process during discharge of aprotic Li–O2 batteries and determines rate, capacity, and reversibility. Current understanding states that the partition between surface adsorbed and dissolved lithium superoxide governs whether Li2O2 grows as a conformal surface film or larger particles, leading to low or high capacities, respectively. However, better understanding governing factors for Li2O2 packing density and capacity requires structural sensitive in situ metrologies. Here, we establish in situ small- and wide-angle X-ray scattering (SAXS/WAXS) as a suitable method to record the Li2O2 phase evolution with atomic to submicrometer resolution during cycling a custom-built in situ Li–O2 cell. Combined with sophisticated data analysis, SAXS allows retrieving rich quantitative structural information from complex multiphase systems. Surprisingly, we find that features are absent that would point at a Li2O2 surface film formed via two consecutive electron transfers, even in poorly solvating electrolytes thought to be prototypical for surface growth. All scattering data can be modeled by stacks of thin Li2O2 platelets potentially forming large toroidal particles. Li2O2 solution growth is further justified by rotating ring-disk electrode measurements and electron microscopy. Higher discharge overpotentials lead to smaller Li2O2 particles, but there is no transition to an electronically passivating, conformal Li2O2 coating. Hence, mass transport of reactive species rather than electronic transport through a Li2O2 film limits the discharge capacity. Provided that species mobilities and carbon surface areas are high, this allows for high discharge capacities even in weakly solvating electrolytes. The currently accepted Li–O2 reaction mechanism ought to be reconsidered.

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“…[5][6][7] The problems would be more serious in sodium-air batteries because these batteries are open systems and the liquid electrolyte tends to evaporate easily, which restricts their further practical application. [8][9][10][11][12][13][14][15] Recently, rechargeable Na-CO 2 batteries have attracted much attention due to their high energy density (1125 W h kg À1 ) and the clean utilization of the greenhouse gas CO 2 . However, such batteries are oen based on liquid or quasi-solid-state electrolytes and plagued by potential safety issues.…”

Section: Introductionmentioning

confidence: 99%

A compatible anode/succinonitrile-based electrolyte interface in all-solid-state Na–CO₂ batteries

et al. 2019

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On the incompatibility of lithium–O₂ battery technology with CO₂

Abstract: The peroxide dianion reacts with CO2 in polar aprotic organic media to afford the hydroperoxycarbonate and carbonate radical anions. These highly reactive species, if formed in lithium–O2 cells, can lead to cell degradation via oxidation of the electrolyte and electrode.

Cited by 33 publications

References 39 publications

Rechargeable Batteries from the Perspective of the Electron Spin

Rechargeable Batteries from the Perspective of the Electron Spin

In situ small-angle X-ray scattering reveals solution phase discharge of Li–O ₂ batteries with weakly solvating electrolytes

A compatible anode/succinonitrile-based electrolyte interface in all-solid-state Na–CO₂ batteries

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On the incompatibility of lithium–O2 battery technology with CO2

Abstract: The peroxide dianion reacts with CO2 in polar aprotic organic media to afford the hydroperoxycarbonate and carbonate radical anions. These highly reactive species, if formed in lithium–O2 cells, can lead to cell degradation via oxidation of the electrolyte and electrode.

Cited by 33 publications

References 39 publications

Rechargeable Batteries from the Perspective of the Electron Spin

Rechargeable Batteries from the Perspective of the Electron Spin

In situ small-angle X-ray scattering reveals solution phase discharge of Li–O 2 batteries with weakly solvating electrolytes

A compatible anode/succinonitrile-based electrolyte interface in all-solid-state Na–CO2 batteries

Contact Info

Product

Resources

About

On the incompatibility of lithium–O₂ battery technology with CO₂

In situ small-angle X-ray scattering reveals solution phase discharge of Li–O ₂ batteries with weakly solvating electrolytes

A compatible anode/succinonitrile-based electrolyte interface in all-solid-state Na–CO₂ batteries