Reactivity of Carbon in Lithium–Oxygen Battery Positive Electrodes

Itkis, Daniil M.; Semenenko, D. A.; Kataev, Elmar Yu.; Belova, Alina I.; Neudachina, Vera S.; Sirotina, Anna P.; Hävecker, Michael; Teschner, Detre; Knop‐Gericke, Axel; Dudin, Pavel; Barinov, A.; Goodilin, Eugene A.; Shao‐Horn, Yang; Yashina, Lada V.

doi:10.1021/nl4021649

Cited by 262 publications

(294 citation statements)

References 31 publications

(55 reference statements)

Supporting

Mentioning

283

Contrasting

Unclassified

Order By: Relevance

“…However, the pre‐filled Li 2 CO 3 and conductive carbon in the above work are rather different from the in situ newly formed Li 2 CO 3 and C, which can be verified from the extremely high charge voltage in the former case. In addition, superoxide radicals not only have great influence on the electrolyte but also corrode the carbon specimens easily 15, 16. Also, it would benefit for understanding the reversibility of Li‐CO 2 batteries if the CO 2 consumption and evolution were confirmed by in situ measurements during discharge and charge processes.…”

mentioning

confidence: 99%

Verifying the Rechargeability of Li‐CO₂ Batteries on Working Cathodes of Ni Nanoparticles Highly Dispersed on N‐Doped Graphene

et al. 2017

View full text Add to dashboard Cite

Li‐CO2 batteries could skillfully combine the reduction of “greenhouse effect” with energy storage systems. However, Li‐CO2 batteries still suffer from unsatisfactory electrochemical performances and their rechargeability is challenged. Here, it is reported that a composite of Ni nanoparticles highly dispersed on N‐doped graphene (Ni‐NG) with 3D porous structure, exhibits a superior discharge capacity of 17 625 mA h g−1, as the air cathode for Li‐CO2 batteries. The batteries with these highly efficient cathodes could sustain 100 cycles at a cutoff capacity of 1000 mA h g−1 with low overpotentials at the current density of 100 mA g−1. Particularly, the Ni‐NG cathodes allow to observe the appearance/disappearance of agglomerated Li2CO3 particles and carbon thin films directly upon discharge/charge processes. In addition, the recycle of CO2 is detected through in situ differential electrochemical mass spectrometry. This is a critical step to verify the electrochemical rechargeability of Li‐CO2 batteries. Also, first‐principles computations further prove that Ni nanoparticles are active sites for the reaction of Li and CO2, which could guide to design more advantageous catalysts for rechargeable Li‐CO2 batteries.

show abstract

mentioning

confidence: 99%

Verifying the Rechargeability of Li‐CO₂ Batteries on Working Cathodes of Ni Nanoparticles Highly Dispersed on N‐Doped Graphene

et al. 2017

View full text Add to dashboard Cite

show abstract

“…11 Intensive research has been done on finding alternative electrolytes and electrode materials that are resistant towards degradation by superoxide. A few solvents like dimethyl sulfoxide 12 , some glymes 13,14 and pyrrolidinium or piperidinium based ionic liquids [15][16][17][18][19] have been identified as promising electrolyte choices.…”

mentioning

confidence: 99%

A new method to prevent degradation of lithium–oxygen batteries: reduction of superoxide by viologen

et al. 2015

View full text Add to dashboard Cite

Lithium-oxygen battery development is hampered by degradation reactions initiated by superoxide, which is formed in the pathway of oxygen reduction to peroxide. This work demonstrates that the superoxide lifetime is drastically decreased upon addition of ethyl viologen, which catalyses the reduction of superoxide to peroxide.Lithium-oxygen batteries can potentially deliver 5 times more energy than lithium-ion batteries of the same weight. [1][2][3][4][5][6][7] The energy is provided by the electrochemical reaction between Li and O2, typically forming Li2O2. Since all these compounds are very light, the mass of the battery can be very small, leading to a high specific energy (i.e. energy per mass). However, several factors hamper the practical performance of current lithium-oxygen batteries. First of all, superoxide is formed as the first product of the reduction of O2: 8,9 O2 + e -+Li + → LiO2(1) It has been shown that superoxide reacts irreversibly with most known electrolytes 10 and it is also probably involved in the corrosion of carbon electrodes. 11 Intensive research has been done on finding alternative electrolytes and electrode materials that are resistant towards degradation by superoxide. A few solvents like dimethyl sulfoxide 12 , some glymes 13, 14 and pyrrolidinium or piperidinium based ionic liquids [15][16][17][18][19] have been identified as promising electrolyte choices. Gold 12 and TiC 20 electrodes have shown much better capacity performance than carbon, in terms of cycling stability and suppression of side reactions. An alternative approach to solve the superoxide problem is the introduction of catalysts to promote the reduction of superoxide to peroxide: LiO2 + e -+Li + → Li2O2(2) This would decrease the lifetime of superoxide and, with this, the long-term durability of the battery. If the superoxide lifetime were short enough, it would be conceivable that a wider range of materials could be incorporated in lithium-oxygen batteries without serious problems of degradation reactions. In addition, such catalysts would also be beneficial in order to speed up the overall 2-electron reduction of oxygen to Li2O2. In the absence of such catalyst, Li2O2 is usually formed by disproportionation of LiO2: 8, 9 2LiO2 →O2+ Li2O2 (3) However, as will be shown below, the rate of this reaction is very slow at low superoxide concentrations. Another important issue in lithium-oxygen batteries is that the discharge product, Li2O2, deposits on the surface of the electrode, blocking its electrochemical activity. This produces a very early end of discharge, with little discharge product being formed, and little capacity being delivered. An innovative solution to solve this problem is the introduction of soluble redox shuttles that can displace the formation of Li2O2 from the electrode surface to the solution, by reducing oxygen through a homogenous chemical reaction. 21,22 Soluble redox couples have also been used as mediators for the evolution of oxygen in lithium-oxygen batteries, resulting in major performance i...

show abstract

“…29 -35 Differential electrochemical mass spectrometry (DEMS) experiments on isotopically labeled 13 30 at the interface between graphene and a solid-state lithium ion conductor (with no nonaqueous electrolyte present). The formation of epoxy groups on the carbon surface and their conversion to carbonates in the presence of LiO 2 was observed and provides direct evidence for carbon instability during battery discharge.…”

Section: Stability Of Inactive Components In the Oxygen Electrodementioning

confidence: 99%

Materials challenges in rechargeable lithium-air batteries

et al. 2014

View full text Add to dashboard Cite

show abstract

Reactivity of Carbon in Lithium–Oxygen Battery Positive Electrodes

Cited by 262 publications

References 31 publications

Verifying the Rechargeability of Li‐CO₂ Batteries on Working Cathodes of Ni Nanoparticles Highly Dispersed on N‐Doped Graphene

Verifying the Rechargeability of Li‐CO₂ Batteries on Working Cathodes of Ni Nanoparticles Highly Dispersed on N‐Doped Graphene

A new method to prevent degradation of lithium–oxygen batteries: reduction of superoxide by viologen

Materials challenges in rechargeable lithium-air batteries

Contact Info

Product

Resources

About

Reactivity of Carbon in Lithium–Oxygen Battery Positive Electrodes

Cited by 262 publications

References 31 publications

Verifying the Rechargeability of Li‐CO2 Batteries on Working Cathodes of Ni Nanoparticles Highly Dispersed on N‐Doped Graphene

Verifying the Rechargeability of Li‐CO2 Batteries on Working Cathodes of Ni Nanoparticles Highly Dispersed on N‐Doped Graphene

A new method to prevent degradation of lithium–oxygen batteries: reduction of superoxide by viologen

Materials challenges in rechargeable lithium-air batteries

Contact Info

Product

Resources

About

Verifying the Rechargeability of Li‐CO₂ Batteries on Working Cathodes of Ni Nanoparticles Highly Dispersed on N‐Doped Graphene

Verifying the Rechargeability of Li‐CO₂ Batteries on Working Cathodes of Ni Nanoparticles Highly Dispersed on N‐Doped Graphene