The electrochemical behavior of 1,3-dioxolane—LiClO4 solutions—II. Contaminated solutions

Aurbach, Doron; Youngman, Orit; Dan, P.

doi:10.1016/0013-4686(90)87056-8

Cited by 85 publications

(70 citation statements)

References 14 publications

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“…Additionally, there might be other Lewis acids in solution, which could help initiating the polymerization as well. Polymerization of DOL has been already shown in Li-O 2 batteries, i.e., where molecular oxygen is present and dissolved in the electrolyte, 17,28 as well as LSB. 26 Aurbach and coworkers 28 showed, for instance, that a silver electrode swept from 3.0 to 1.7 V vs Li/Li + in a 0.5 mol L −1 solution of LiClO 4 in DOL do not show any polymerization product over its surface.…”

Section: Resultsmentioning

confidence: 99%

“…Polymerization of DOL has been already shown in Li-O 2 batteries, i.e., where molecular oxygen is present and dissolved in the electrolyte, 17,28 as well as LSB. 26 Aurbach and coworkers 28 showed, for instance, that a silver electrode swept from 3.0 to 1.7 V vs Li/Li + in a 0.5 mol L −1 solution of LiClO 4 in DOL do not show any polymerization product over its surface. For the same system with added O 2 , some polyether species are detected on the silver surface by FTIR, showing that the products of O 2 reduction can indeed promote DOL polymerization, although the specific mechanism of polymerization in this setup was not determined.…”

Section: Resultsmentioning

confidence: 99%

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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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Section: Resultsmentioning

confidence: 99%

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 addition, the energy-dispersive X-ray spectrometry elemental mappings in Figure S9 revealed the uniform distribution of N (28.21 atom %) on the discharged cathode; the N content was also reduced to 4 atom % after charging, indicating the decomposition of N 2 fixation products and consistent with the FT-IR results ( Figure 2F). 28,29 The concentration of Li 3 N in N 2 fixation and N 2 evolution reactions was monitored with a UV-vis spectrometer by colorimetry. 30 It is known that Li 3 N reacts with water immediately to form NH 3 as follows: and the NH 2 Hg 2 OI complex presents a light absorption at 425 nm.…”

Section: Resultsmentioning

confidence: 99%

Reversible Nitrogen Fixation Based on a Rechargeable Lithium-Nitrogen Battery for Energy Storage

Bao

Shi

et al. 2017

Chem

158

102

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Based on a rechargeable lithium-nitrogen battery, an advanced strategy for reversible nitrogen fixation and energy conversion has been successfully implemented at room temperature and atmospheric pressure. It shows a promising nitrogen fixation faradic efficiency and superior cyclability. SUMMARYAlthough the availability of nitrogen (N 2 ) from the atmosphere for N 2 fixation is limitless, it is immensely challenging to artificially fix N 2 at ambient temperature and pressure given the element's chemical inertness and stability. In this article, as a proof-of-concept experiment, we report on the successful implementation of a reversible N 2 cycle based on a rechargeable lithium-nitrogen (Li-N 2 ) battery with the proposed reversible reaction of 6Li + N 2 ! 2Li 3 N. The assembled N 2 fixation battery system, consisting of a Li anode, ether-based electrolyte, and a carbon cloth cathode, shows a promising electrochemical faradic efficiency (59%). The unique properties of Li-N 2 rechargeable batteries not only provide promising candidates for N 2 fixation but also enable an advanced N 2 /Li 3 N cycle strategy for next-generation electrochemical energy-storage systems.

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“…where n is the cycle number (20), Q c the involved lithium charge (2.07 mAh/cm 2 ), Q 0 the initial lithium charge of working electrode, and Q f the residual lithium charge of working electrode. Lithium bisperfluoroethylsulfonyl imide (LiN(SO 2 C 2 F 5 ) 2 ) electrolytes with five-, six-, and seven-membered cycloalkane solvents containing two oxygen atoms were characterized in order to develop the organic electrolytes for 4 V lithium metal rechargeable batteries.…”

Section: Methodsmentioning

confidence: 99%

Lithium Imide Electrolytes with Two-Oxygen-Atom-Containing Cycloalkane Solvents for 4 V Lithium Metal Rechargeable Batteries

Wang

Yasukawa

Kasuya

2000

J. Electrochem. Soc.

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Though much effort has been paid for lithium metal rechargeable batteries with lithium metal as anode in the past decades, 1-6 its commercial application is not yet realized. This has been attributed to the interface reaction of freshly deposited lithium with inorganic and organic species in the electrolytes, which results in low lithium cycling efficiency, deleterious dendritic morphology of deposited lithium surface, and safety concern. Therefore, finding electrolytes with low reactivity with lithium metal is an important issue in the effort to realize the commercial application of lithium metal rechargeable batteries.So far, tetrahydrofuran (THF) and its alkyl derivative electrolytes with LiAsF 6 or LiClO 4 as solute was explored mainly to suppress the reaction of lithium anode with electrolytes. 11-17 1,3-Dioxolane (DOL) based electrolytes also received special attention due to high lithium cycling efficiency in this electrolyte. 18-21 Nevertheless, the poor anodic stability of THF-based solvents and DOL solvent led to the application of these electrolytes only in 3 V lithium metal rechargeable batteries. 11,13,14 The toxicity of LiAsF 6 and the safety problems of LiClO 4 also limited the practical application of these electrolytes.In recent work, we developed 1 mol/dm 3 LiN(SO 2 C 2 F 5 ) 2 /EC ϩ tetrahydropyran (THP) (5:5) electrolyte. [22][23][24][25][26] This electrolyte was found to have many advantages, such as a high lithium cycling efficiency of >99%, good oxidation stability, satisfactory boiling point, and promising thermal stability. The Li/LiMn 2 O 4 coin cell with this electrolyte also gave excellent cycling performance. Furthermore, scanning electron microscopy (SEM) observation showed that the deposited lithium in this electrolyte had fine particle morphology rather than dendritic morphology. Other groups have also studied the use of lithium imide salts for lithium rechargeable batteries. 27-30 Naoi et al. reported the good surface morphology of deposited lithium and high lithium cycling efficiency in LiN(SO 2 C 2 F 5 ) 2 electrolytes. 31 The main problems inherent in the practical application of 1 mol/dm 3 LiN(SO 2 C 2 F 5 ) 2 /EC ϩ THP (5:5) electrolyte are poor lowtemperature performance (freezing point: 8ЊC) and low boiling point of THP solvent. To solve this problem, we studied LiN(SO 2 C 2 F 5 ) 2 electrolytes with DOL, 1,3-dioxane (DOX), 1,3-dioxepane (DOXP) and their alkyl derivatives as solvents in this work. ExperimentalElectrolyte preparation.- Table I lists the examined solutes and five-, six-, and seven-membered cycloalkane solvents with two oxygen atoms. These solvents were generally used with a purity of >99% after being purified by distillation. Lithium bistrifluoromethylsulfonyl imide (LiN(SO 2 CF 3 ) 2 ) and LiN(SO 2 C 2 F 5 ) 2 solutes were dried at 130ЊC and under vacuum for 24 h, while LiPF 6 solute was used as received due to its high purity (battery grade). The preparation of electrolytes was performed in an argon glove box. The water content in the resultant electrolytes...

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The electrochemical behavior of 1,3-dioxolane—LiClO4 solutions—II. Contaminated solutions

Cited by 85 publications

References 14 publications

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

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

Reversible Nitrogen Fixation Based on a Rechargeable Lithium-Nitrogen Battery for Energy Storage

Lithium Imide Electrolytes with Two-Oxygen-Atom-Containing Cycloalkane Solvents for 4 V Lithium Metal Rechargeable Batteries

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