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Mixed LiCo(0.6)M(0.4)PO(4) (M = Mn, Fe, Ni) phosphates: cycling mechanism and thermal stability
Natalia N Bramnik1, Dmytro M Trots, Heiko J Hofmann
1Institute for Materials Science, University of Technology, Petersenstr. 23, 64287, Darmstadt, Germany. bramnik@tu-darmstadt.de
Abstract:
The electrochemical delithiation of LiCo(0.6)M(0.4)PO(4) phosphates (M = Mn, Fe, Ni) was studied by in situ synchrotron diffraction. In all three metallophosphates the oxidation-reduction of 3d-elements proceed via two-phase mechanisms leading to two-phase regions, corresponding to the Co(2+)/Co(3+) and M(2+)/M(3+) reactions. The Ni(2+)/Ni(3+) reaction was not revealed, neither by the potentiostatic intermittent titration technique (PITT) nor by diffraction. In the two-phase reaction, the olivine-like structure of the cathode remains preserved, which is characteristic of this type of materials. Pronounced solid-solution domains were observed during both lithium extraction and insertion. The thermal stability of the charged cathodes is limited by the presence of Co(3+) and its intrinsic instability in these compounds.
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