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1.
Nat Mater ; 21(12): 1412-1418, 2022 Dec.
Article in English | MEDLINE | ID: mdl-36109675

ABSTRACT

Solid-state batteries are seen as key to the development of safer and higher-energy-density batteries, by limiting flammability and enabling the use of the lithium metal anode, respectively. Composite polymer-ceramic electrolytes are a possible solution for their realization, by benefiting from the combined mechanical properties of the polymer electrolyte and the thermal stability and high conductivity of the ceramic electrolyte. In this study we used different liquid electrolyte chemistries as models for the polymer electrolytes, and evaluated the effect of adding a variety of porous and dense ceramic electrolytes on the conductivity. All the results could be modelled with the effective medium theory, allowing prediction of the conductivity of electrolyte combinations. We unambiguously determined that highly conductive porous particles act as insulators in such systems, whereas dense particles act as conductors, thereby advancing our understanding of composite electrolyte conductivity.

2.
Chem Commun (Camb) ; 55(84): 12711-12714, 2019 Oct 17.
Article in English | MEDLINE | ID: mdl-31588448

ABSTRACT

The electrochemically generated CuIICuIII mixed-valence species promotes activation of strong aliphatic C-H bonds (i.e. toluene) at room temperature. The mechanistic pathway turns from stoichiometric to catalytic upon addition of base, hence demonstrating that such high-valence dicopper species can be key reactive intermediates in copper-based oxidative processes.

3.
Inorg Chem ; 57(19): 12364-12375, 2018 Oct 01.
Article in English | MEDLINE | ID: mdl-30226767

ABSTRACT

A (µ-hydroxido, µ-phenoxido)CuIICuII complex 1 has been synthesized using an unsymmetrical ligand bearing an N, N-bis(2-pyridyl)methylamine (BPA) moiety coordinating one copper and a dianionic bis-amide moiety coordinating the other copper(II) ion. Electrochemical mono-oxidation of the complex in DMF occurs reversibly at 213 K at E1/2 = 0.12 V vs Fc+/Fc through a metal-centered process. The resulting species (complex 1+) is only stable at low temperature and has been spectroscopically characterized by UV-vis-NIR cryo-spectroelectrochemical and EPR methods. DFT and TD-DFT calculations, consistent with experimental data, support the formation of a CuIICuIII phenoxido-hydroxido complex. Low-temperature chemical oxidation of 1 by NOSbF6 yields a tetranuclear complex 2(SbF6)(NO2) which displays two binuclear CuIICuII subunits. The X-ray crystal structure of 2(SbF6)(NO2) evidences that the nitrogen of the terminal amide group is protonated and the coordination of the amide occurs via the O atom. The bis-amide moiety appears to be a non-innocent proton acceptor along the redox process. Alternatively, protonation of complex 1 leads to the complex 2(ClO4)2, as evidenced by X-ray crystallography, cyclic voltammetry, and 1H NMR.

4.
Inorg Chem ; 55(17): 8263-6, 2016 Sep 06.
Article in English | MEDLINE | ID: mdl-27518211

ABSTRACT

Bis(µ-hydroxo)dicopper(II,II) bearing a naphthyridine-based ligand has been synthesized and characterized in the solid state and solution. Cyclic voltammetry at room temperature displays a reversible redox system that corresponds to the monoelectronic oxidation of the complex. Spectroscopic and time-resolved spectroelectrochemical data coupled to theoretical results support the formation of a charge-localized mixed-valent Cu(II,III)2 species.

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