Toward a Lithium–“Air” Battery: The Effect of CO<sub>2</sub> on the Chemistry of a Lithium–Oxygen Cell

Lim, Hyung‐Kyu; Lim, Hyeon‐Sook; Park, Kyu‐Young; Seo, Dong‐Hwa; Gwon, Hyeokjo; Hong, Jihyun; Goddard, William A.; Kim, Hyungjun; Kang, Kisuk

doi:10.1021/ja4016765

Cited by 320 publications

(275 citation statements)

References 47 publications

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“…4. All the measurements were conducted with a capacity limit of 500 mAh g −1 in accordance with a commonly-used technique8202122. The charge cut-off voltage was set at the voltage after rise observed in Fig.…”

Section: Resultsmentioning

confidence: 99%

All-solid-state lithium-oxygen battery with high safety in wide ambient temperature range

Kitaura

Zhou

2015

Sci Rep

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There is need to develop high energy storage devices with high safety to satisfy the growing industrial demands. Here, we show the potential to realize such batteries by assembling a lithium-oxygen cell using an inorganic solid electrolyte without any flammable liquid or polymer materials. The lithium-oxygen battery using Li1.575Al0.5Ge1.5(PO4)3 solid electrolyte was examined in the pure oxygen atmosphere from room temperature to 120 °C. The cell works at room temperature and first full discharge capacity of 1420 mAh g−1 at 10 mA g−1 (based on the mass of carbon material in the air electrode) was obtained. The charge curve started from 3.0 V, and that the majority of it lay below 4.2 V. The cell also safely works at high temperature over 80 °C with the improved battery performance. Furthermore, fundamental data of the electrochemical performance, such as cyclic voltammogram, cycle performance and rate performance was obtained and this work demonstrated the potential of the all-solid-state lithium-oxygen battery for wide temperature application as a first step.

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Section: Resultsmentioning

confidence: 99%

All-solid-state lithium-oxygen battery with high safety in wide ambient temperature range

Kitaura

Zhou

2015

Sci Rep

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“…However, low round-trip efficiency and poor cycle life caused by high overpotential during charge process limit their practical application5678. One of the most important reasons responsible for the irreversible side reaction is the instability of carbon-based cathode9101112.…”

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Compatible interface design of CoO-based Li-O2 battery cathodes with long-cycling stability

Shang

Dong

et al. 2015

Sci Rep

107

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Lithium-oxygen batteries with high theoretical energy densities have great potential. Recent studies have focused on different cathode architecture design to address poor cycling performance, while the impact of interface stability on cathode side has been barely reported. In this study, we introduce CoO mesoporous spheres into cathode, where the growth of crystalline discharge products (Li2O2) is directly observed on the CoO surface from aberration-corrected STEM. This CoO based cathode demonstrates more than 300 discharge/charge cycles with excessive lithium anode. Under deep discharge/charge, CoO cathode exhibited superior cycle performance than that of Co3O4 with similar nanostructure. This improved cycle performance can be ascribed to a more favorable adsorption configuration of Li2O2 intermediates (LiO2) on CoO surface, which is demonstrated through DFT calculation. The favorable adsorption of LiO2 plays an important role in the enhanced cycle performance, which reduced the contact of LiO2 to carbon materials and further alleviated the side reactions during charge process. This compatible interface design may provide an effective approach in protecting carbon-based cathodes in metal-oxygen batteries.

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“…14, 15 The formation of parasitic by-products in Li-O 2 batteries (which have been found to form extensively on charging due to cathode and electrolyte instabilities) is a major hurdle to their widespread implementation. 16,17 The nature of Li 2 O 2 (i.e morphology, crystallinity, size and location on the cathode) formed during discharge, and its impact on capacity, cycle life and charging behavior has attracted recent research interest.…”

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Examining the Role of Electrolyte and Binders in Determining Discharge Product Morphology and Cycling Performance of Carbon Cathodes in Li-O₂Batteries

Geaney

O’Dwyer

2015

J. Electrochem. Soc.

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In this report we examine the influence of electrode binder and electrolyte solvent on the electrochemical response of carbon based Li-O 2 battery cathodes. Much higher discharge capacities were noted for cathodes discharged in DMSO compared to TEGDME. The increased capacities were related to the large spherical discharge products formed in DMSO. Characteristic toroids which have been noted in TEGDME electrolytes previously were not observed due to the low water content of the electrolyte. Linear voltage sweeps were used to investigate ORR in both of the solvents for each of the binder systems (PVDF, PVP, PEO and PTFE) and related to the Li 2 O 2 formed on the cathode surfaces. Galvanostatic tests were also conducted in air as a comparison with the pure O 2 environment typically used for Li-O 2 battery testing. Interestingly, tests for the two electrolytes showed opposite trends in terms of discharge capacity values with capacities increased in TEGDME (compared to those seen in O 2 ) and decreased in DMSO. The report highlights the key roles of electrolyte and cathode composition in determining the stability of Li-O 2 batteries and highlights the importance of identifying more stable electrolyte/cathode pairings. Li-O 2 batteries are an exciting class of energy storage devices with exceptional theoretical capacities which could facilitate longrange electrical vehicles if fully optimized systems are realized. [1][2][3][4][5] Energy storage in Li-O 2 batteries proceeds via different mechanisms to those associated with conventional Li-ion batteries, necessitating detailed studies into the fundamental processes associated with discharge and charge.6-8 It has been shown in a number of studies that the energy storage mechanism for Li-O 2 batteries involves the reversible formation/decomposition of Li 2 O 2 upon discharge and charge respectively.9-13 While the O 2 required to form Li 2 O 2 during discharge can theoretically be provided from ambient air, the majority of systems investigated to date have used pure O 2 to avoid unwanted side-reactions due to the ingress of atmospheric CO 2 and H 2 O.14,15 The formation of parasitic by-products in Li-O 2 batteries (which have been found to form extensively on charging due to cathode and electrolyte instabilities) is a major hurdle to their widespread implementation. 16,17 The nature of Li 2 O 2 (i.e morphology, crystallinity, size and location on the cathode) formed during discharge, and its impact on capacity, cycle life and charging behavior has attracted recent research interest.18-20 A number of reports have presented the formation of Li 2 O 2 toroids on cathode surfaces during discharge in a variety of cathode/electrolyte systems. 7,8,12,19,[21][22][23][24][25] Adams et al. showed that the formation of these toroids was related to the applied current for a given system (TEGDME/LiTFSI electrolyte and Super P carbon cathode). 26Their results suggested that low applied currents tend to favor the formation of large crystalline Li 2 O 2 toroids on the cathode surface with ...

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Toward a Lithium–“Air” Battery: The Effect of CO₂ on the Chemistry of a Lithium–Oxygen Cell

Cited by 320 publications

References 47 publications

All-solid-state lithium-oxygen battery with high safety in wide ambient temperature range

All-solid-state lithium-oxygen battery with high safety in wide ambient temperature range

Compatible interface design of CoO-based Li-O2 battery cathodes with long-cycling stability

Examining the Role of Electrolyte and Binders in Determining Discharge Product Morphology and Cycling Performance of Carbon Cathodes in Li-O₂Batteries

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Toward a Lithium–“Air” Battery: The Effect of CO2 on the Chemistry of a Lithium–Oxygen Cell

Cited by 320 publications

References 47 publications

All-solid-state lithium-oxygen battery with high safety in wide ambient temperature range

All-solid-state lithium-oxygen battery with high safety in wide ambient temperature range

Compatible interface design of CoO-based Li-O2 battery cathodes with long-cycling stability

Examining the Role of Electrolyte and Binders in Determining Discharge Product Morphology and Cycling Performance of Carbon Cathodes in Li-O2Batteries

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Product

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Toward a Lithium–“Air” Battery: The Effect of CO₂ on the Chemistry of a Lithium–Oxygen Cell

Examining the Role of Electrolyte and Binders in Determining Discharge Product Morphology and Cycling Performance of Carbon Cathodes in Li-O₂Batteries