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Enhanced Electrochemical Performance of LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> Composite Cathodes for Lithium-Ion Batteries by Selective Doping of K<sup>+</sup>/Cl<sup>−</sup> and K<sup>+</sup>/F<sup>−</sup>
oleh: Aijia Wei, Jinping Mu, Rui He, Xue Bai, Xiaohui Li, Lihui Zhang, Yanji Wang, Zhenfa Liu, Suning Wang
Format: | Article |
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Diterbitkan: | MDPI AG 2021-09-01 |
Deskripsi
K<sup>+</sup>/Cl<sup>−</sup> and K<sup>+</sup>/F<sup>−</sup> co-doped LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> (LNMO) materials were successfully synthesized via a solid-state method. Structural characterization revealed that both K<sup>+</sup>/Cl<sup>−</sup> and K<sup>+</sup>/F<sup>−</sup> co-doping reduced the Li<i><sub>x</sub></i>Ni<sub>1</sub><sub>−</sub><i><sub>x</sub></i>O impurities and enlarged the lattice parameters compared to those of pure LNMO. Besides this, the K<sup>+</sup>/F<sup>−</sup> co-doping decreased the Mn<sup>3+</sup> ion content, which could inhibit the Jahn–Teller distortion and was beneficial to the cycling performance. Furthermore, both the K<sup>+</sup>/Cl<sup>−</sup> and the K<sup>+</sup>/F<sup>−</sup> co-doping reduced the particle size and made the particles more uniform. The K<sup>+</sup>/Cl<sup>−</sup> co-doped particles possessed a similar octahedral structure to that of pure LNMO. In contrast, as the K<sup>+</sup>/F<sup>−</sup> co-doping amount increased, the crystal structure became a truncated octahedral shape. The Li<sup>+</sup> diffusion coefficient calculated from the CV tests showed that both K<sup>+</sup>/Cl<sup>−</sup> and K<sup>+</sup>/F<sup>−</sup> co-doping facilitated Li<sup>+</sup> diffusion in the LNMO. The impedance tests showed that the charge transfer resistances were reduced by the co-doping. These results indicated that both the K<sup>+</sup>/Cl<sup>−</sup> and the K<sup>+</sup>/F<sup>−</sup> co-doping stabilized the crystal structures, facilitated Li<sup>+</sup> diffusion, modified the particle morphologies, and increased the electrochemical kinetics. Benefiting from the unique advantages of the co-doping, the K<sup>+</sup>/Cl<sup>−</sup> and K<sup>+</sup>/F<sup>−</sup> co-doped samples exhibited improved rate and cycling performances. The K<sup>+</sup>/Cl<sup>−</sup> co-doped Li<sub>0.97</sub>K<sub>0.03</sub>Ni<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>3.97</sub>Cl<sub>0.03</sub> (LNMO-KCl0.03) exhibited the best rate capability with discharge capacities of 116.1, 109.3, and 93.9 mAh g<sup>−1</sup> at high C-rates of 5C, 7C, and 10C, respectively. Moreover, the K<sup>+</sup>/F<sup>−</sup> co-doped Li<sub>0.98</sub>K<sub>0.02</sub>Ni<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>3.98</sub>F<sub>0.02</sub> (LNMO-KF0.02) delivered excellent cycling stability, maintaining 85.8% of its initial discharge capacity after circulation for 500 cycles at 5C. Therefore, the K<sup>+</sup>/Cl<sup>−</sup> or K<sup>+</sup>/F<sup>−</sup> co-doping strategy proposed herein will play a significant role in the further construction of other high-voltage cathodes for high-energy LIBs.