Effects of Mg Doping at Different Positions in Li-Rich Mn-Based Cathode Material on Electrochemical Performance

Li-rich Mn-based layered oxides are among the most promising cathode materials for next-generation lithium-ion batteries, yet they suffer from capacity fading and voltage decay during cycling. The electrochemical performance of the material can be improved by doping with Mg. However, the effect of Mg doping at different positions (lithium or transition metals) remains unclear. Li1.2Mn0.54Ni0.13Co0.13O2 (LR) was synthesized by coprecipitation followed by a solid-state reaction. The coprecipitation stage was used to introduce Mg in TM layers (sample LR-Mg), and the solid-state reaction (st) was used to dope Mg in Li layers (LR-Mg(st)). The presence of magnesium at different positions was confirmed by XRD, XPS, and electrochemical studies. The investigations have shown that the introduction of Mg in TM layers is preferable in terms of the electrochemical performance. The sample doped with Mg at the TM positions shows better cyclability and higher discharge capacity than the undoped sample. The poor electrochemical properties of the sample doped with Mg at Li positions are due to the kinetic hindrance of oxidation of the manganese-containing species formed after activation of the Li2MnO3 component of the composite oxide. The oxide LR-Mg(st) demonstrates the lowest lithium-ion diffusion coefficient and the greatest polarization resistance compared to LR and LR-Mg.

The Synergetic Effect Induced High Electrochemical Performance of CuO/Cu2O/Cu Nanocomposites as Lithium-Ion Battery Anodes

Due to the high theoretical capability, copper-based oxides were widely investigated. A facile water bath method was used to synthesis CuO nanowires and CuO/Cu2O/Cu nanocomposites. Owing to the synergetic effect, the CuO/Cu2O/Cu nanocomposites exhibit superior electrochemical performance compared to the CuO nanowires. The initial discharge and charge capacities are 2,660.4 mAh/g and 2,107.8 mAh/g, and the reversible capacity is 1,265.7 mAh/g after 200 cycles at 200 mA/g. Moreover, the reversible capacity is 1,180 mAh/g at 800 mA/g and 1,750 mAh/g when back to 100 mA/g, indicating the excellent rate capability. The CuO/Cu2O/Cu nanocomposites also exhibit relatively high electric conductivity and lithium-ion diffusion coefficient, especially after cycling. For the energy storage mechanism, the capacitive controlled mechanism is predominance at the high scan rates, which is consistent with the excellent rate capability. The outstanding electrochemical performance of the CuO/Cu2O/Cu nanocomposites indicates the potential application of copper-based oxides nanomaterials in future lithium-ion batteries.

Investigation of Lithium Ion Diffusion of Graphite Anode by the Galvanostatic Intermittent Titration Technique

Graphite is used as a state-of-the-art anode in commercial lithium-ion batteries (LIBs) due to its highly reversible lithium-ion storage capability and low electrode potential. However, graphite anodes exhibit sluggish diffusion kinetics for lithium-ion intercalation/deintercalation, thus limiting the rate capability of commercial LIBs. In order to determine the lithium-ion diffusion coefficient of commercial graphite anodes, we employed a galvanostatic intermittent titration technique (GITT) to quantify the quasi-equilibrium open circuit potential and diffusion coefficient as a function of lithium-ion concentration and potential for a commercial graphite electrode. Three plateaus are observed in the quasi-equilibrium open circuit potential curves, which are indicative of a mixed phase upon lithium-ion intercalation/deintercalation. The obtained diffusion coefficients tend to increase with increasing lithium concentration and exhibit an insignificant difference between charge and discharge conditions. This study reveals that the diffusion coefficient of graphite obtained with the GITT (1 × 10−11 cm2/s to 4 × 10−10 cm2/s) is in reasonable agreement with literature values obtained from electrochemical impedance spectroscopy. The GITT is comparatively simple and direct and therefore enables systematic measurements of ion intercalation/deintercalation diffusion coefficients for secondary ion battery materials.

Twin boundary defect engineering improves lithium-ion diffusion for fast-charging spinel cathode materials

Defect engineering on electrode materials is considered an effective approach to improve the electrochemical performance of batteries since the presence of a variety of defects with different dimensions may promote ion diffusion and provide extra storage sites. However, manipulating defects and obtaining an in-depth understanding of their role in electrode materials remain challenging. Here, we deliberately introduce a considerable number of twin boundaries into spinel cathodes by adjusting the synthesis conditions. Through high-resolution scanning transmission electron microscopy and neutron diffraction, the detailed structures of the twin boundary defects are clarified, and the formation of twin boundary defects is attributed to agminated lithium atoms occupying the Mn sites around the twin boundary. In combination with electrochemical experiments and first-principles calculations, we demonstrate that the presence of twin boundaries in the spinel cathode enables fast lithium-ion diffusion, leading to excellent fast charging performance, namely, 75% and 58% capacity retention at 5 C and 10 C, respectively. These findings demonstrate a simple and effective approach for fabricating fast-charging cathodes through the use of defect engineering.