Reaction mechanisms for the limited reversibility of Li–O2 chemistry in organic carbonate electrolytes

Xu, Wu; Xu, Kang; Viswanathan, Vilayanur V.; Towne, Silas A.; Hardy, John S.; Xiao, Jie; Nie, Zimin; Hu, Dehong; Wang, Deyu; Zhang, Ji‐Guang

doi:10.1016/j.jpowsour.2011.06.099

Cited by 204 publications

(210 citation statements)

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“…Following this study, several researchers were able to determine the mechanism by which carbonate-based electrolyte decomposition occurs. [ 67,[69][70][71][72][73] For example, Zhang et al [ 73 ] carried out density functional theory (DFT) calculations and determined that the ring opening of PC in the presence of solvated species such as O 2 − , LiO 2 , LiO 2 − , and Li 2 O 2 has no energy barriers ( Figure 3 ), facilitating the formation of Li 2 CO 3 and lithium alkylcarbonate. The presence of these compounds was confi rmed by Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS).…”

Section: Carbonate-based Electrolytesmentioning

confidence: 99%

“…[ 73 ] Together with Li 2 CO 3 , C 3 H 6 (OCO 2 Li) 2 , CH 3 CO 2 Li, and HCO 2 Li, Bruce and co-workers [ 67 ] also identifi ed CO 2 and H 2 O as discharge products of a PC-based lithium/ air cell by using FTIR, nuclear magnetic resonance (NMR) and surface-enhanced Raman spectroscopy (SERS), together with differential electrochemical mass spectrometry (DEMS). Zhang and co-workers [ 72 ] used X-ray diffraction (XRD) and DEMS to confi rm the formation of Li 2 CO 3 during the discharge process and the evolution of CO 2 during charging.…”

Section: Carbonate-based Electrolytesmentioning

confidence: 99%

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The Lithium/Air Battery: Still an Emerging System or a Practical Reality?

et al. 2014

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gas. At the same time, the penetration of renewable energy sources has opened up the possibility of creating a CO 2 -neutral mobility system, where electric vehicles are powered by wind, hydro, and solar energy.Broad fi nancial efforts are being made at a governmental and industrial level to fund research into new areas of energy storage. The U.S. Department of Energy has allocated $20 million to energy storage research in 2012 and $15 million the following year, while the German government has committed itself to ¤200 million between 2011 and 2018; [ 1 ] similar schemes are also being promoted in Japan by the New Energy and Industrial Technology Development Organization (NEDO). The EU-backed "Horizon 2020" program aims at funding research into energy storage technologies, a fi eld where the European Union lags behind the U.S. and East Asia. [ 2 ] Lithium-ion technology has established itself as a type of reliable energy-storage chemistry over the past 20 years, fi rst being used in camcorders, then mobile phones, laptops, and more recently electric cars. However, as the size of the battery pack increases, so does the belief that the cost per kW h and its energy density are not suitable for practical vehicle applications. The Tesla Model S, which sports a 400 km driving range, does so with a whopping 85 kW h battery pack that alone has up to twice the price of a standard economy car. With a current cost higher than 400 $ kW h −1 , electric cars have so far only entered a niche, high-end market where users are willing to pay a premium. Resizing the battery pack, and so the total cost of an electric car, results in a limited driving range (typically 100-150 km) that automatically restricts the use for long-haul journeys and triggers the so-called "range anxiety" feeling. For these reasons, the need to develop energy-storage technologies that enable at least a 500 km driving range, while retaining the same battery pack volume at an affordable price, is of primary interest for governments and car manufacturers. A Brief History of Lithium/Air BatteriesOver the years, the scientifi c community has focused its interest on advanced lithium-ion and fuel cells with only incremental improvements being made. Lithium-ion technology in particular is predicted to reach an asymptotic limit in specifi c Lithium/air is a fascinating energy storage system. The effective exploitation of air as a battery electrode has been the long-time dream of the battery community. Air is, in principle, a no-cost material characterized by a very high specifi c capacity value. In the particular case of the lithium/air system, energy levels approaching that of gasoline have been postulated. It is then not surprising that, in the course of the last decade, great attention has been devoted to this battery by various top academic and industrial laboratories worldwide. This intense investigation, however, has soon highlighted a series of issues that prevent a rapid development of the Li/air electrochemical system. Although several breakthroughs have be...

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Section: Carbonate-based Electrolytesmentioning

confidence: 99%

Section: Carbonate-based Electrolytesmentioning

confidence: 99%

The Lithium/Air Battery: Still an Emerging System or a Practical Reality?

et al. 2014

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“…The analogous Li/O2 system provides support for this strategy, as it is now well established that cells that discharge to Li2O2 can be reversed with the application of moderate potentials, while those that form Li2O cannot. 13,[21][22][23] MgO2 is stable up to tem- Figure 1. Theoretical specific energies (per mass of discharge product) of selected metal-oxygen chemistries (blue and grey bars) compared to Li-ion (red bar).…”

Section: Introductionmentioning

confidence: 99%

Theoretical Limiting Potentials in Mg/O₂ Batteries

et al. 2016

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ABSTRACT:A rechargeable battery based on a multi-valent Mg/O2 couple is an attractive chemistry due to its high theoretical energy density and potential for low cost. Nevertheless, metal-air batteries based on alkaline earth anodes have received limited attention and generally exhibit modest performance. In addition, many fundamental aspects of this system remain poorly understood, such as the reaction mechanisms associated with discharge and charging. The present study aims to close this knowledge gap and thereby accelerate the development of Mg/O2 batteries by employing first-principles calculations to characterize electrochemical processes on the surfaces of likely discharge products, MgO and MgO2. Thermodynamic limiting potentials for charge and discharge are calculated for several scenarios, including variations in surface stoichiometry and the presence/absence of intermediate species in the reaction pathway. The calculations indicate that pathways involving oxygen intermediates are preferred, as they generally result in higher discharge and lower charging voltages. In agreement with recent experiments, cells that discharge to MgO exhibit low round-trip efficiencies, which are rationalized by the presence of large thermodynamic overvoltages. In contrast, MgO2-based cells are predicted to be much more efficient: superoxide-terminated facets on MgO2 crystallites enable low overvoltages and round-trip efficiencies approaching 90%. These data suggest that the performance of Mg/O2 batteries can be dramatically improved by biasing discharge towards the formation of MgO2 rather than MgO.

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“…Although cell failure due to Li dendrite formation has been extensively studied for Li-ion battery application 15 , it is not clear if such a mechanism is applicable to the Li-O 2 batteries because of the differences in the cell construction, materials and operating environments. At present, the studies on the cyclability and stability of Li-O 2 batteries have been primarily focused on the cathode catalysts [16][17][18][19][20][21][22][23][24][25][26][27][28][29] , electrolytes [30][31][32][33][34][35][36][37][38][39][40][41][42][43][44] , binder 45 and so on. For example, the electrolyte decomposition was found during the cycling of Li-O 2 batteries, which led to the formation of by-products such as H 2 O, CO 2 , insoluble Li salts, and the eventual degradation of the cathode and the separator [33][34][35][36][46][47][48][49][50][51] .…”

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confidence: 99%

Reversibility of anodic lithium in rechargeable lithium–oxygen batteries

et al. 2013

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Non-aqueous lithium-air batteries represent the next-generation energy storage devices with very high theoretical capacity. The benefit of lithium-air batteries is based on the assumption that the anodic lithium is completely reversible during the discharge-charge process. Here we report our investigation on the reversibility of the anodic lithium inside of an operating lithium-air battery using spatially and temporally resolved synchrotron X-ray diffraction and three-dimensional micro-tomography technique. A combined electrochemical process is found, consisting of a partial recovery of lithium metal during the charging cycle and a constant accumulation of lithium hydroxide under both charging and discharging conditions. A lithium hydroxide layer forms on the anode separating the lithium metal from the separator. However, numerous microscopic 'tunnels' are also found within the hydroxide layer that provide a pathway to connect the metallic lithium with the electrolyte, enabling sustained iontransport and battery operation until the total consumption of lithium.

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Reaction mechanisms for the limited reversibility of Li–O2 chemistry in organic carbonate electrolytes

Cited by 204 publications

References 20 publications

The Lithium/Air Battery: Still an Emerging System or a Practical Reality?

The Lithium/Air Battery: Still an Emerging System or a Practical Reality?

Theoretical Limiting Potentials in Mg/O₂ Batteries

Reversibility of anodic lithium in rechargeable lithium–oxygen batteries

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Reaction mechanisms for the limited reversibility of Li–O2 chemistry in organic carbonate electrolytes

Cited by 204 publications

References 20 publications

The Lithium/Air Battery: Still an Emerging System or a Practical Reality?

The Lithium/Air Battery: Still an Emerging System or a Practical Reality?

Theoretical Limiting Potentials in Mg/O2 Batteries

Reversibility of anodic lithium in rechargeable lithium–oxygen batteries

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Theoretical Limiting Potentials in Mg/O₂ Batteries