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加速亚纳米孔中的充电动力学。

Accelerating charging dynamics in subnanometre pores.

出版信息

Nat Mater. 2014 Apr;13(4):387-93. doi: 10.1038/nmat3916.

Abstract

Supercapacitors have exceptional power density and cyclability but smaller energy density than batteries. Their energy density can be increased using ionic liquids and electrodes with subnanometre pores, but this tends to reduce their power density and compromise the key advantage of supercapacitors. To help address this issue through material optimization, here we unravel the mechanisms of charging subnanometre pores with ionic liquids using molecular dynamics simulations, navigated by a phenomenological model. We show that charging of ionophilic pores is a diffusive process, often accompanied by overfilling followed by de-filling. In sharp contrast to conventional expectations, charging is fast because ion diffusion during charging can be an order of magnitude faster than in the bulk, and charging itself is accelerated by the onset of collective modes. Further acceleration can be achieved using ionophobic pores by eliminating overfilling/de-filling and thus leading to charging behaviour qualitatively different from that in conventional, ionophilic pores.

摘要

超级电容器具有卓越的功率密度和循环寿命,但能量密度却低于电池。通过使用离子液体和具有亚纳米孔的电极,可以提高超级电容器的能量密度,但这往往会降低其功率密度,并损害超级电容器的关键优势。为了通过材料优化来解决这个问题,我们使用分子动力学模拟并辅以唯象模型,揭示了离子液体在亚纳米孔中的充电机制。我们表明,亲孔的充电是一个扩散过程,通常伴随着过充随后是去充。与传统的预期形成鲜明对比的是,充电速度很快,因为充电过程中的离子扩散速度可能比本体中快一个数量级,并且充电本身会由于集体模式的出现而加速。通过使用疏孔,可以消除过充/去充,从而实现进一步的加速,并导致与传统的亲孔中截然不同的充电行为。

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