3 V manganese oxide electrode materials for lithium batteries. Page: 4 of 20
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3 V Manganese Oxide Electrode Materials for Lithium Batteries
C. S. Johnson* and M. M. Thackeray,
Electrochemical Technology Program,
Chemical Technology Division,
Argonne National Laboratory
Argonne, Illinois 60439, USA
Specific discharge capacities in excess of 200 mAh/g and good reversible cycling behavior
between 3.8 and 2.0 V has been observed in a lithium cell for a-MnO2 phases with the hollandite
structure. A combination of lithia (Li2O) doping and ammonia (NH3) treatment of the active
material powder having the composition a-[0.143 Li201 "[0.007 NH3] 'MnO2 gave the best
electrochemical performance in liquid organic electrolyte (1:1 EC:DMC, 1 M LiPF6) coin cells,
with metallic Li as the negative electrode. The added lithia forms a defect close-packed array of
oxide anions and stabilizes the interior of the 2x2 tunnel of the hollandite structure by partially
filling the crystallographic position (0,0,0.5) of the tetragonal unit cell (I4/m) with 02, from the
added Li20. Ammonia treatment is hypothesized to partially fill other lattice vacancies still
available within the 2x2 tunnel with the nitrogen atoms from NH3 taking the same position as
the oxide anion in the array. The NH3 can further stabilize the cell during lithium
insertion/extraction because of its favorable hydrogen bonding ability and Lewis base
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Johnson, C. S. & Thackeray, M. M. 3 V manganese oxide electrode materials for lithium batteries., article, June 20, 2000; Illinois. (digital.library.unt.edu/ark:/67531/metadc711713/m1/4/: accessed January 19, 2019), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.