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Chemistry

1,3,5-Triphenylbenzene and Corannulene as Electron Receptors for Lithium Solvated Electron Solutions

Published: October 10th, 2016

DOI:

10.3791/54366

1Energy Research Institute (ERI@N), Nanyang Technological University, 2School of Materials Science and Engineering, Nanyang Technological University, 3School of Physical and Mathematical Sciences, Nanyang Technological University

The authors report on conductivity studies carried out on lithium solvated electron solutions (LiSES) prepared using 1,3,5-triphenylbenzene (TPB) and corannulene as electron receptors.

The authors report on conductivity studies carried out on lithium solvated electron solutions (LiSES) prepared using two types of polyaromatic hydrocarbons (PAH), namely 1,3,5-triphenylbenzene and corannulene, as electron receptors. The solid PAHs were first dissolved in tetrahydrofuran (THF) to form a solution. Metallic lithium was then dissolved into these PAH/THF solutions to yield either blue or greenish blue solutions, colors which are indicative of the presence of solvated electrons. Conductivity measurements at ambient temperature carried out on 1,3,5-triphenylbenzene-based LiSES, denoted by LixTPB(THF)24.7 (x = 1, 2, 3, 4), showed an increase of conductivity with increase of Li:PAH ratio from x = 1 to 2. However, the conductivity gradually decreased upon further increasing the ratio. Indeed the conductivity of LixTPB(THF)24.7 for x = 4 is even lower than for x = 1. Such behavior is similar to that of the previously reported LiSES prepared from biphenyl and naphthalene. Conductivity versus temperature measurements on corannulene-based LiSES, denoted by LixCor(THF)247 (x = 1, 2, 3, 4, 5), showed linear relationships with negative slopes, indicating a metallic behavior similar to biphenyl and naphthalene-based LiSES.

Lithium solvated electron solutions (LiSES) prepared using simple two-ring polyaromatic hydrocarbons (PAH) such as biphenyl and naphthalene can potentially be utilized as liquid anodes in refuelable lithium cells1-7. In the LiSES, these simple PAH molecules served as the electron receptors for solvated electrons from dissolved metallic lithium.

Progressing from these two-ring systems, the authors have since then carried out conductivity measurement studies on LiSES which are prepared using more complex PAHs, starting with the group of cyclopenta-2,4-dienone derivatives8. These PAHs include larger PAHs (>two benzene....

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1. Preparation Procedure for 1,3,5-Triphenylbenzene (1)

  1. Place a mixture of acetophenone (4.0 g, 33.3 mmol) and 100 ml of absolute ethanol into a round bottom three neck 250 ml flask equipped with magnetic stirrer, reflux condenser, nitrogen inlet, bubbler, dropping funnel and thermometer. Add silicon tetrachloride (11.9 g, 8.0 ml, 70.2 mmol, 2.1 eq.) to the mixture in one portion at 0 °C under nitrogen using the dropping funnel.
  2. Observe the evolution of gaseous hydrogen chloride for 10 min. The.......

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Reaction between various amounts of lithium and mixtures of 1,3,5-triphenylbenzene with THF gives greenish blue or deep blue colored solutions as shown in Figure 2. A light color indicates that the particular sample of LiSES has a low concentration of solvated electrons. 1,3,5-triphenylbenzene demonstrates increase of conductivity with increase of Li:PAH ratio from 1 to 2 in 0.5 M THF solution (Table 1). However, conductivity value gradually decreases upon further increasing the molar ra.......

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For the 1,3,5-triphenylbenzene-based LiSES, a sample with a light color shows that it has a low concentration of solvated electrons. LixTPB(THF)24.7 (for x = 1, 2, 3, 4) demonstrates a behavior in its conductivity versus x similar to that seen for LiSES made from biphenyl and naphthalene1, 2.There is an initial increase in conductivity with increase of Li:PAH ratio from 1 to 2 and a subsequent decrease in conductivity upon further increasing the molar ratio to 3 and 4, with condu.......

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The authors acknowledge funding from the Singapore Ministry of Education Tier 2 Research Fund (project MOE2013-T2-2-002) for this project.

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Name Company Catalog Number Comments
Biphenyl Reagentplus, 99.5% Sigma Aldrich B34656-1KG
Tetrahydrofuran Anhydrous, 99.9%, Inhibi Sigma Aldrich 401757-100ML
Iodine, Anhydrous, Beads, -10 Mesh, 99.999% trace metals basis  Sigma Aldrich 451045-25G
Lithium iodide, anhydrous, 99.95% (metals basis) Alfa Aesar 40666
Lithium Ion Conducting Glass ceramics (Diameter 1" x 150 mm)  Ohara LICGC(AG01)
Lithium Foil  Alfa Aesar 010769.14
Methanol anhydrous, 99.8% Sigma Aldrich 322415-100ML 
CompactStat : Electrochemical Analyser with Impedance Ivium Technologies Not Applicable
Cond 3310 Conductivity Meter WTW Not Applicable
Digital Multimeter, Model Fluke 179 Fluke Corporation Not Applicable
1,3,5-triphenylbenzene Synthesized from acetpohenone according to procedure described in literature
Silicon tetrachloride Sigma Aldrich 215120-100G
acetophenone TCI A0061-500g
Ethanol Merck Millipore 1.00983.2511

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