New Battery Electrolytes for Low and High Temperatures: Liquid and Solid Ammoniates for High Energy Batteries: I . Sodium Iodide and Lithium Perchlorate Ammoniates

Badoz-Lambling, J.; Bardin, M.; Bérnard, C.; Fahys, Bernard; Herlem, M.; Thiébault, A.; Robert, Guy

doi:10.1149/1.2095662

Cited by 17 publications

(19 citation statements)

References 8 publications

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“…Despite that the NaI‐3.3 NH 3 electrolyte was initially designed by Badoz‐Lambing et al. for use in primary batteries, [ 54 ] Martinez et al. more recently repurposed these for secondary batteries.…”

Section: Stabilizing the Na Anode–electrolyte Interphasementioning

confidence: 99%

Room‐Temperature Sodium–Sulfur Batteries and Beyond: Realizing Practical High Energy Systems through Anode, Cathode, and Electrolyte Engineering

Eng

Kumar

Zhang

et al. 2021

Advanced Energy Materials

123

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The increasing energy demands of society today have led to the pursuit of alternative energy storage systems that can fulfil rigorous requirements like cost‐effectiveness and high storage capacities. Based fundamentally on earth‐abundant sodium and sulfur, room‐temperature sodium–sulfur batteries are a promising solution in applications where existing lithium‐ion technology remains less economically viable, particularly in large‐scale stationary systems such as grid‐level storage. Here, the key challenges in the field are first highlighted, followed by comprehensive analyses of accessible strategies to overcome them, starting from engineering of the anode–electrolyte interface in both liquid and solid electrolytes. Recently reported polymer and solid‐state electrolytes are also surveyed. Thereafter, the core principles guiding use‐inspired design of cathode architectures, covering the spectrum of elemental sulfur and polysulfide cathodes, to emerging host structures, and covalent composites are focused upon. Future prospects are explored, with insights into other alkali‐metal systems beyond sodium–sulfur batteries, such as the potassium–sulfur battery. Finally a conclusion is provided by outlining the research directions necessary to attain high energy sodium–sulfur devices, and potential solutions to issues concerning large‐scale production, so as to ultimately realize widespread deployment of practical energy storage systems.

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Section: Stabilizing the Na Anode–electrolyte Interphasementioning

confidence: 99%

Room‐Temperature Sodium–Sulfur Batteries and Beyond: Realizing Practical High Energy Systems through Anode, Cathode, and Electrolyte Engineering

Eng

Kumar

Zhang

et al. 2021

Advanced Energy Materials

123

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“…1,2 The solution was transferred to a glove box, and TiI 4 ͑Aldrich͒ was added in order to get a 3.5 ϫ 10 Ϫ3 mol L Ϫ1 solution.…”

Section: Methodsmentioning

confidence: 99%

“…In fact, sodium is insoluble in this electrolyte and remains stable for months. 2 Its surface stays bright and no precipitation of sodium amide is observed. As metallic titanium is also a strong reducing compound, it seemed feasible to prepare Ti͑0͒ from TiI 4 in solution in NaI•3.3 NH 3 .…”

mentioning

confidence: 99%

“…This ammoniate is liquid at room temperature under a NH 3 pressure of 0.5 bar and is conveniently prepared. 1,2 It has a wide electrochemical window from Ϫ2.2 V ͑sodium deposition͒ up to ϩ0.6 V vs. SRE, silver reference electrode ͑oxidation of I Ϫ ions to I 3 Ϫ ions͒. Due to the high concentration of Na ϩ ions ͑7.8 M͒, solvated electrons do not exist.…”

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confidence: 99%

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Cathodic Behavior of Liquid Ammonia Solutions of Titanium Tetraiodide at Room Temperature

Herlem

Fantini

Tran-Van

et al. 2001

J. Electrochem. Soc.

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TiI 4 is soluble in the liquid ammoniate NaI•3.3NH 3 . Ti͑IV͒ can be reduced to Ti͑III͒ at a smooth Pt electrode at Ϫ1.63 V vs. ferrocene/ferricinium (͓Fc͔ 0/ϩ ) couple. This reduction seems to be a quasi-reversible reaction. No further reduction to metallic titanium is observed.We describe the electrochemistry of titanium͑IV͒, added as TiI 4 , in the ammoniate NaI•3.3NH 3 . This ammoniate is liquid at room temperature under a NH 3 pressure of 0.5 bar and is conveniently prepared. 1,2 It has a wide electrochemical window from Ϫ2.2 V ͑sodium deposition͒ up to ϩ0.6 V vs. SRE, silver reference electrode ͑oxidation of I Ϫ ions to I 3 Ϫ ions͒. Due to the high concentration of Na ϩ ions ͑7.8 M͒, solvated electrons do not exist. In fact, sodium is insoluble in this electrolyte and remains stable for months. 2 Its surface stays bright and no precipitation of sodium amide is observed. As metallic titanium is also a strong reducing compound, it seemed feasible to prepare Ti͑0͒ from TiI 4 in solution in NaI•3.3 NH 3 . To our knowledge, the electrochemical behavior of Ti ions has not been experimentally studied in liquid ammonia. 3,4 Only computations of the standard electrode potential for Ti͑IV͒/Ti͑III͒ were done. Bratsch and Lagowski 4 found 0.5 V vs. SHE at 298 K, but Ti͑IV͒ was as Ti 3 N 4 in the presence of protons (NH 4 ϩ ions͒. This paper describes the cathodic behavior of TiI 4 in the neutral and unbuffered medium NaI•3.3NH 3 . ExperimentalNaI•3.3NH 3 ͑density 1.6 at 293 K͒ was prepared by reacting gaseous NH 3 ͑Air Liquide, electronic quality͒ with solid anhydrous NaI ͑Aldrich͒ at room temperature. 1,2 The solution was transferred to a glove box, and TiI 4 ͑Aldrich͒ was added in order to get a 3.5 ϫ 10 Ϫ3 mol L Ϫ1 solution.The electrochemical setup was described elsewhere. 5 The working electrode was a smooth Pt disk ͑1 mm diam͒. The counter electrode was a Pt wire. The SRE was a silver wire isolated in a separated compartment containing only NaI•3.3NH 3 .The UV-visible ͑UV-vis͒ spectrometry was performed with a Beckman DU 650 spectrometer. The thin optical cell ͑0.1 cm͒ was carefully dried under an argon stream before filling it with the solution. Results and DiscussionTiI 4 dissolves readily in the ammoniate and yields a strong purple color after a few minutes. In about 10 min, the solution undergoes a discoloration concomitant with the appearance of a white precipitate. Figure 1 shows the UV-vis spectrum. The absorption peak at 362 nm is characteristic of TiI 4 . One can estimate the extinction coefficient, ⑀ ⑀ ϭ 8.5 ϫ 10 2 mol Ϫ1 L cm Ϫ1 Cyclic voltammetry was performed on the solution before its discoloration and after the complete dissolution of TiI 4 . The voltammetric curve at a Pt electrode exhibited two cathodic peaks at Ϫ0.85 and Ϫ1.10 V vs. SRE. With time, the first peak disappeared while the second increased, which corresponds to proton reduction ͑see Fig. 2͒. This proton reduction peak prevented the observation of other possible peaks at more negative potentials; therefore, no reduction to metallic Ti...

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“…Relatively recently it has become apparent that some low melting ammoniates of various sodium (and lithium) salts do not dissolve or react with the relevant alkali metal and possess low ammonia pressures in the temperature range 25 -200° C (1,2). Further, some ofthese materials'appe&i to have relatively large electrochemical stability windows, in the range 0-2.5 V vs. the alkali metal, and high conductivities for the alkali metal ions.…”

Section: Possible Negative Electrode I Electrolyte Modificationsmentioning

confidence: 99%

New battery materials: Final report

Huggins¹

1989

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New Battery Electrolytes for Low and High Temperatures: Liquid and Solid Ammoniates for High Energy Batteries: I . Sodium Iodide and Lithium Perchlorate Ammoniates

Cited by 17 publications

References 8 publications

Room‐Temperature Sodium–Sulfur Batteries and Beyond: Realizing Practical High Energy Systems through Anode, Cathode, and Electrolyte Engineering

Room‐Temperature Sodium–Sulfur Batteries and Beyond: Realizing Practical High Energy Systems through Anode, Cathode, and Electrolyte Engineering

Cathodic Behavior of Liquid Ammonia Solutions of Titanium Tetraiodide at Room Temperature

New battery materials: Final report

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