Journal
JOURNAL OF MATERIALS CHEMISTRY
Volume 22, Issue 34, Pages 17773-17781Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2jm33346e
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Funding
- National Science Foundation for Distinguished Young Scholars of China [51025209]
- Outstanding Young Scholar Grant at Jiangsu Province [2008023]
- National Nature Science Foundation of China [21103089]
- Key Projects in Nature Science Foundation of Jiangsu Province [BK2011030]
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It is believed that a TiN coating can increase the electrical conductivity, and consequently the performance, of an electrode. In this work, a simple one-step synthesis of nitrogen- and TiN-modified Li4Ti5O12, i.e. solid-state reaction of Li2CO3 and TiO2 anatase in an ammonia-containing atmosphere, is introduced. The reducing ammonia atmosphere could cause the partial reduction of Ti4+ to Ti3+ and the doping of nitrogen into the Li4Ti5O12 lattice, in addition to the formation of the TiN phase. By controlling the ammonia concentration of the atmosphere and using a slight Ti excess in the reactants, Li4Ti5O12, nitrogen- doped Li4Ti5O12, or TiN-coated nitrogen-doped Li4Ti5O12 were obtained. Both the electrical conductivity and the TiN thickness were closely related to the ammonia concentration in the atmosphere. Synthesis under reducing atmosphere also resulted in powders with a different plate shape particulate morphology from that synthesized in air, and such plate-shape powders had an ultrahigh tap density of similar to 1.9 g cm(-3). Interestingly, the formation of TiN was not beneficial for capacity improvement due to its insulation towards lithium ions, unlike the nitrogen doping. The sample prepared under 3% NH3-N-2, which was free of TiN coating, showed the best electrode performance with a capacity of 103 mA h g(-1) even at 20 C with only 3% capacity decay after cycling 100 times.
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