Low temperature rechargeable batteries are important to life in cold climates, polar/deep‐sea expeditions, and space explorations. Here, this work reports 3.5–4 V rechargeable lithium/chlorine (Li/Cl2) batteries operating down to −80 °C, employing Li metal negative electrode, a novel carbon dioxide (CO2) activated porous carbon (KJCO2) as the positive electrode, and a high ionic conductivity (≈5–20 mS cm−1from −80 °C to room‐temperature) electrolyte comprised of aluminum chloride (AlCl3), lithium chloride (LiCl), and lithium bis(fluorosulfonyl)imide (LiFSI) in low‐melting‐point (−104.5 °C) thionyl chloride (SOCl2). Between room‐temperature and −80 °C, the Li/Cl2battery delivers up to ≈29 100–4500 mAh g−1first discharge capacity (based on carbon mass) and a 1200–5000 mAh g−1reversible capacity over up to 130 charge–discharge cycles. Mass spectrometry and X‐ray photoelectron spectroscopy probe Cl2trapped in the porous carbon upon LiCl electro‐oxidation during charging. At −80 °C, Cl2/SCl2/S2Cl2generated by electro‐oxidation in the charging step are trapped in porous KJCO2carbon, allowing for reversible reduction to afford a high discharge voltage plateau near ≈4 V with up to ≈1000 mAh g−1capacity for SCl2/S2Cl2reduction and up to ≈4000 mAh g−1capacity at ≈3.1 V plateau for Cl2reduction.
In the Mn3O4electrode, chloride ions are reversibly converted into atomic chlorine species. Trapped Zn2+cations aid in stabilizing these chlorine atoms in polychloride species.
more » « less- PAR ID:
- 10537398
- Publisher / Repository:
- RSC
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 14
- Issue:
- 44
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 12645 to 12652
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Searching for a connection between the two‐electron redox behavior of Group‐14 elements and their possible use as platforms for the photoreductive elimination of chlorine, we have studied the photochemistry of [(
o ‐(Ph2P)C6H4)2GeIVCl2]PtIICl2and [(o ‐(Ph2P)C6H4)2ClGeIII]PtIIICl3, two newly isolated isomeric complexes. These studies show that, in the presence of a chlorine trap, both isomers convert cleanly into the platinum germyl complex [(o ‐(Ph2P)C6H4)2ClGeIII]PtICl with quantum yields of 1.7 % and 3.2 % for the GeIV–PtIIand GeIII–PtIIIisomers, respectively. Conversion of the GeIV–PtIIisomer into the platinum germyl complex is a rare example of a light‐induced transition‐metal/main‐group‐element bond‐forming process. Finally, transient‐absorption‐spectroscopy studies carried out on the GeIII–PtIIIisomer point to a ligand arene–Cl.charge‐transfer complex as an intermediate. -
Abstract Searching for a connection between the two‐electron redox behavior of Group‐14 elements and their possible use as platforms for the photoreductive elimination of chlorine, we have studied the photochemistry of [(
o ‐(Ph2P)C6H4)2GeIVCl2]PtIICl2and [(o ‐(Ph2P)C6H4)2ClGeIII]PtIIICl3, two newly isolated isomeric complexes. These studies show that, in the presence of a chlorine trap, both isomers convert cleanly into the platinum germyl complex [(o ‐(Ph2P)C6H4)2ClGeIII]PtICl with quantum yields of 1.7 % and 3.2 % for the GeIV–PtIIand GeIII–PtIIIisomers, respectively. Conversion of the GeIV–PtIIisomer into the platinum germyl complex is a rare example of a light‐induced transition‐metal/main‐group‐element bond‐forming process. Finally, transient‐absorption‐spectroscopy studies carried out on the GeIII–PtIIIisomer point to a ligand arene–Cl.charge‐transfer complex as an intermediate. -
Rationale Building on our report that collision‐induced dissociation (CID) can be used to create the highly reactive U‐alkylidyne species [O=U≡CH]+, our goal was to determine whether the species could be as an intermediate for synthesis of [OUS]+by reaction with carbon disulfide (CS2).
Methods Cationic uranyl‐propiolate precursor ions were generated by electrospray ionization, and multiple‐stage CID in a linear trap instrument was used to prepare [O=U≡CH]+. Neutral CS2was admitted into the trap through a modified He inlet and precision leak valves.
Results The [O=U≡CH]+ion reacts with CS2to generate [OUS]+. CID of [OUS]+causes elimination of the axial sulfide ligand to generate [OU]+. Using isotopically labeled reagent, we found that [OUS]+reacts with O2to create [UO2]+.
Conclusions [O=U≡CH]+proves to be a useful reagent ion for synthesis of [OUS]+, a species that to date has only been created by gas‐phase reactions of U+and U2+. Dissociation of [OUS]+to create [OU]+, but not [US]+, and the efficient conversion of the species into [UO2]+, is consistent with the relative differences in U–O and U–S bond energies.
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