School of Mines, China University of Mining and Technology, Xuzhou, China.
Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Information Science & Technology University, Beijing, China.
PLoS One. 2022 Jun 2;17(6):e0269086. doi: 10.1371/journal.pone.0269086. eCollection 2022.
Four types of flowerlike manganese dioxide in nano scale was synthesized via a liquid phase method in KMnO4-H2SO4 solution and Cu particles, wherein the effect of Cu particles was investigated in detail. The obtained manganese dioxide powder was characterized by XRD, SEM and TEM, and the supercapacity properties of MnO2 electrode materials were measured. The results showed that doping carbon black can benefit to better dispersion of copper particles, resulting in generated smaller size of Cu particles, and the morphology of MnO2 nanoparticles was dominated by that of Cu particles. The study of MnO2 synthesis by different sources of Cu particles showed that the size of MnO2 particles decreased significantly with freshly prepared fine copper powder compared with using commercial Cu powder, and the size of MnO2 particles can be further reduced to 120 nm by prepared Cu particles with smaller size. Therefore, it was suggested that the copper particles served as not only the reductant and but also the nuclei centre for the growth of MnO2 particles in synthesis process MnO2, and that is the reason how copper particles worked on the growth of flower-like MnO2 and electrochemical property. In the part of investigation for electrochemical property, the calculated results of b values indicated that the electrode materials have pseudo capacitance property, and the highest specific capacitance of 197.2 F g-1 at 2 mV s-1 and 148 F/g at 1 A/g were obtained for MCE electrode materials (MnO2 was synthesized with freshly prepared copper particles, where carbon black was used and dispersed in ethanol before preparation of Cu particles). The values of charge transfer resistance in all types of MnO2 materials electrodes were smaller than 0.08 Ω. The cycling retention of MCE material electrode is still kept as 93.8% after 1000 cycles.
四种纳米花状二氧化锰通过在 KMnO4-H2SO4 溶液和 Cu 颗粒中的液相法合成,其中详细研究了 Cu 颗粒的作用。通过 XRD、SEM 和 TEM 对所得的二氧化锰粉末进行了表征,并测量了 MnO2 电极材料的超级电容性能。结果表明,掺杂炭黑有利于更好地分散铜颗粒,从而生成更小尺寸的 Cu 颗粒,并且 MnO2 纳米颗粒的形态主要由 Cu 颗粒的形态决定。通过不同来源的 Cu 颗粒合成 MnO2 的研究表明,与使用商业 Cu 粉相比,使用新制备的细铜粉可使 MnO2 颗粒的尺寸显著减小,并且通过制备更小尺寸的 Cu 颗粒可以进一步将 MnO2 颗粒的尺寸减小至 120nm。因此,有人认为铜颗粒不仅是 MnO2 颗粒合成过程中的还原剂,而且还是 MnO2 颗粒生长的核中心,这就是铜颗粒如何作用于花状 MnO2 的生长和电化学性能的原因。在电化学性能研究部分,b 值的计算结果表明,电极材料具有赝电容特性,对于 MCE 电极材料(MnO2 是使用新制备的铜颗粒合成的,其中炭黑在制备 Cu 颗粒之前分散在乙醇中),在 2 mV s-1 时的最高比电容为 197.2 F g-1,在 1 A/g 时的比电容为 148 F/g。所有类型的 MnO2 材料电极的电荷转移电阻值均小于 0.08 Ω。在 1000 次循环后,MCE 材料电极的循环保持率仍保持在 93.8%。