Oxide chemistry and electroreduction of NO3− in molten alkali nitrates

Zambonin, P. G.

doi:10.1016/s0022-0728(70)80159-0

Cited by 56 publications

(25 citation statements)

References 18 publications

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“…The reduction is not peak-shaped (in contrast with NaNO 3 melts), [7][8][9]11 but the onset of the reduction occurs well before the edge of the RTIL solvent window. A current of approximately À240 nA was chosen as a limiting value for reversal of the voltammetric sweep.…”

Section: Resultsmentioning

confidence: 93%

“…Five distinctive peaks are observed, and the identities of peaks i to v are suggested in Table 1, based on similar observations in NaNO 3 melts. [7][8][9] We propose that the peak observed at À1.67 V vs. Ag in Fig. 6 corresponds to the oxidation of sodium oxide (Na 2 O) to sodium peroxide (Na 2 O 2 ), which is followed at À0.52 V by the oxidation of sodium peroxide to sodium superoxide (NaO 2 ), and further by the oxidation of sodium superoxide to molecular oxygen at +0.06 V. We also suggest that peak iv at +0.87 V vs. Ag is the oxidation of sodium nitrite (NaNO 2 ), since a separate study of NaNO 2 in [C 2 mim][NTf 2 ] (not shown here) showed an oxidation peak in almost the same position vs. a silver quasi-reference electrode (QRE).…”

Section: Resultsmentioning

confidence: 99%

“…Many researchers have reported the catalysed electrochemical reduction of nitrate ions in acidic media, 2,5 but the mechanisms proposed are complicated by the presence of protons from the solvent. Several other reports [6][7][8][9] have focused on the cyclic voltammetry obtained from melts of several nitrate salts. The main advantage of studying a melt is that the solution is not contaminated by any proton donor species, or by any supporting electrolyte, since the solutions are intrinsically conductive (made entirely of ions).…”

Section: Introductionmentioning

confidence: 99%

“…In acidic solutions, 2,5 the reaction occurs in the presence of protons, which catalyse the reaction and lead to the formation of water, as opposed to the oxide ion. However, when the ions are in a proton deficient environment, such as in a melt, several authors [7][8][9] have suggested the formation of oxide, peroxide and superoxide species of the corresponding cations (e.g. lithium, sodium and potassium), following the reduction.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

The electrochemical oxidation and reduction of nitrate ions in the room temperature ionic liquid [C₂mim][NTf₂]; the latter behaves as a ‘melt’ rather than an ‘organic solvent’

et al. 2007

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Section: Resultsmentioning

confidence: 93%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

The electrochemical oxidation and reduction of nitrate ions in the room temperature ionic liquid [C₂mim][NTf₂]; the latter behaves as a ‘melt’ rather than an ‘organic solvent’

et al. 2007

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“…10 However, there has been some studies on nitrate reduction in molten-salt electrolytes 27 where the reduction occurs through the formation of lower nitrogen oxides and alkali metal oxides. Since ether-based electrolytes are aprotic, it is expected that the reduction of LiNO 3 follows a mechanism close to that occurring in molten salts (Figure 4b).…”

Section: Resultsmentioning

confidence: 99%

Radical Decomposition of Ether-Based Electrolytes for Li-S Batteries

Lodovico¹,

Varzi²,

Passerini³

2017

J. Electrochem. Soc.

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In this work, the stability of ether-based electrolytes for Li-S batteries is investigated with particular regard to the effect of dissolved oxygen. Specifically, the performance of two different electrolyte solvents, i.e., 1,2-dimethoxyethane and its mixture with 1,3-dioxolane (DME:DOL, 1:1 v/v), is characterized in cells assembled in dry air environment, which would substantially lower production costs with respect to inert atmosphere (Ar). Although stability of all the components would suggest that Li-S batteries built in both the environments should behave similarly, it is found that cells containing the DME:DOL-based electrolyte are rather unstable in the presence of O 2 in contrast to those employing DME-based electrolyte, which show a relatively good performance. The different sensitivity toward O 2 of these electrolytes is associated to the ring-opening reaction of DOL, which happens to a greater extent when O 2 is present, but occurs also in its absence. Based on these results a mechanism for electrolyte degradation in Li-S cells, and its reaction with dissolved polysulfides is proposed, which rationally explain for the first time the behavior already reported in literature for these kind of batteries. These findings are also relevant to the field of Li-O 2 batteries, where these ether-based electrolytes are also used. Sulfur has been extensively investigated as a new cathode material for secondary batteries, in order to replace metal oxides normally used in lithium-ion batteries (LIBs). The first point of interest is its high theoretical specific capacity, around 1672 mAh g −1 , but, as a raw material sulfur is also non-toxic, readily available, and very inexpensive. It is indeed one of the main side products of crude oil refining, with more than 60 million tons produced annually.1 Even the relatively low operating voltage of sulfur-based cathodes, at around 2 V vs. Li/Li + , can be considered as a potential advantage, making it intrinsically safer. 2 Furthermore, the high specific gravimetric capacity of sulfur enables the remarkable specific energy of about 2600 W h kg −1 . However, Lithium-Sulfur batteries (LSB) still present some specific challenges that need to be solved to enable their commercialization.2 First, sulfur has a very low electrical conductivity, around 5 × 10 −30 S cmat 25• C, requiring the introduction of a conductive matrix, normally carbon-based. The carbon host is generally electrochemically inert, such that it decreases the energy density of the electrode as whole, especially since it is often near to 50 wt% of the total sulfur-composite mass. Secondly, and most importantly, sulfur is a conversion material undergoing several chemical transformations during discharge and forming a variety of different polysulfides with the formal oxidation state of sulfur changing from 0 to −2. Some of these intermediate species are soluble in the electrolyte, and very reactive toward both the electrolyte itself 3,4 and the lithium metal anode. 2,5 Most importantly though, their dissolution cause...

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Liquid Salts for Reactions

Johnson

Pagni

2012

Kirk-Othmer Encyclopedia of Chemical Technology

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Organic reactions in room temperature liquid salts have received considerable attention in the last two decades, many of which are highlighted in the short review. Organic reactions occurring in high temperature liquid salts, a topic neglected in the last two decades, are also highlighted. The review will help the interested researcher in choosing a solvent in which to carry out a particular transformation.

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Oxide chemistry and electroreduction of NO3− in molten alkali nitrates

Cited by 56 publications

References 18 publications

The electrochemical oxidation and reduction of nitrate ions in the room temperature ionic liquid [C₂mim][NTf₂]; the latter behaves as a ‘melt’ rather than an ‘organic solvent’

The electrochemical oxidation and reduction of nitrate ions in the room temperature ionic liquid [C₂mim][NTf₂]; the latter behaves as a ‘melt’ rather than an ‘organic solvent’

Radical Decomposition of Ether-Based Electrolytes for Li-S Batteries

Liquid Salts for Reactions

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Oxide chemistry and electroreduction of NO3− in molten alkali nitrates

Cited by 56 publications

References 18 publications

The electrochemical oxidation and reduction of nitrate ions in the room temperature ionic liquid [C2mim][NTf2]; the latter behaves as a ‘melt’ rather than an ‘organic solvent’

The electrochemical oxidation and reduction of nitrate ions in the room temperature ionic liquid [C2mim][NTf2]; the latter behaves as a ‘melt’ rather than an ‘organic solvent’

Radical Decomposition of Ether-Based Electrolytes for Li-S Batteries

Liquid Salts for Reactions

Contact Info

Product

Resources

About

The electrochemical oxidation and reduction of nitrate ions in the room temperature ionic liquid [C₂mim][NTf₂]; the latter behaves as a ‘melt’ rather than an ‘organic solvent’

The electrochemical oxidation and reduction of nitrate ions in the room temperature ionic liquid [C₂mim][NTf₂]; the latter behaves as a ‘melt’ rather than an ‘organic solvent’