通过NMR和EPR光谱学确定原始电池电解质溶液中溶解过渡金属的协调
Jennifer P Allen1,2, Conrad Szczuka3,4, Holly E Smith1
1Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, Cambridge, UK. cpg27@cam.ac.uk.
在离子电池电解质中的过渡金属离子溶解使用EPR和NMR进行了研究. 乙烯碳酸盐 (EC) 主要协调Mn2+和Ni2+,第二个球体是PF6.
科学领域:
- 电化学 电化学 电化学
- 材料科学 材料科学 材料科学
- 物理化学 物理化学
背景情况:
- 了解过渡金属离子溶解对于离子电池的寿命至关重要.
- 目前对这些溶解球的实验性表征是有限的.
- 金属离子的溶解,沉积和反应性显著影响电池的降解.
研究的目的:
- 在Mn2+和Ni2+溶解球中识别协调物种.
- 为了研究 LiPF6/LiTFSI-碳酸盐电解质溶液中的溶解.
- 探测离子复杂化,结合状态和动态.
主要方法:
- 脉冲电子磁共振 (EPR) 谱学用于研究冷的电解质.
- 偏磁核磁共振 (NMR) 谱学用于在环境温度下研究液体电解质.
- 检查电子-核自旋相互作用以探测溶解.
主要成果:
- 乙烯碳酸盐 (EC) 是Mn2+和Ni2+的主要协调溶剂.
- PF6 - - 离子主要位于第二个协调球.
- 接触离子配对发生,特别是在低EC度下.
- Mn2+显示了比TFSI-更强的对PF6-的协调;Ni2+显示了相反的趋势.
结论:
- 这项研究为实验确定电池电解质中偏磁金属的协调球提供了一个框架.
- 这些发现提高了对离子电池性能和降解的溶解效应的理解.
- 阐明了特定的离子-溶剂和离子-离子相互作用,为电解质设计提供了洞察力.
更多相关视频
07:55Elemental-sensitive Detection of the Chemistry in Batteries through Soft X-ray Absorption Spectroscopy and Resonant Inelastic X-ray Scattering
Published on: April 17, 2018
11:44Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds
Published on: October 18, 2018
相关概念视频
Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
Valence Bond Theory
Properties of Transition Metals
Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
Extraction: Advanced Methods
Ladder Diagrams: Redox Equilibria
Consider the Fe3+/Fe2+ half-reaction, which has a standard-state potential of +0.771 V. At potentials more positive than +0.771 V, Fe3+ predominates, whereas Fe2+...
