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Large Polarization of Li4Ti5O12 Lithiated to 0 V at Large Charge/Discharge Rates

Han, Cuiping, He, Yan-Bing, Wang, Shuan, Wang, Chao, Du, Hongda, Qin, Xianying, Lin, Zhiqun, Li, Baohua, Kang, Feiyu
ACS applied materials 2016 v.8 no.29 pp. 18788-18796
batteries, electrochemistry, energy density, impedance, reaction kinetics
The ability to enhance the specific capacity of Li₄Ti₅O₁₂ (LTO) is of practical significance and offers the opportunity to increase the energy density of a full LTO-based battery. Widening the discharge cutoff voltage to 0 V is an effective way to increase the capacity of LTO at low current density. However, whether the specific capacity of LTO at large current rates can be enhanced remains largely unknown. Herein, intriguingly, we found that, when cycled down to 0 V (i.e., from 1.0−2.5 to 0−25 V), LTO exhibited greatly enhanced specific capacity at low rates (<5 C), while it showed a rapid capacity fading and a greatly increased charge/discharge potential gap at high rates (>10 C). The decreased lithium-ion diffusion caused by extra lithium-ion intercalation together with increased internal impedance significantly enhances the polarization and reduces the electrochemical reaction kinetics, which, in turn, hinders the lithiation reaction from LTO to Li₇Ti₅O₁₂ and further to Li₉Ti₅O₁₂.