Kadyk Thomas, Eikerling Michael
Simon Fraser University, Department of Chemistry, 8888 University Drive, Burnaby, BC V5A 1S6, Canada.
Phys Chem Chem Phys. 2015 Aug 14;17(30):19834-43. doi: 10.1039/c5cp02977e.
The possibility of correlating the magnetic susceptibility to the oxidation state of the porous active mass in a chemical or electrochemical reactor was analyzed. The magnetic permeability was calculated using a hierarchical model of the reactor. This model was applied to two practical examples: LiFePO4 batteries, in which the oxidation state corresponds with the state-of-charge, and cyclic water gas shift reactors, in which the oxidation state corresponds to the depletion of the catalyst. In LiFePO4 batteries phase separation of the lithiated and delithiated phases in the LiFePO4 particles in the positive electrode gives rise to a hysteresis effect, i.e. the magnetic permeability depends on the history of the electrode. During fast charge or discharge, non-uniform lithium distributionin the electrode decreases the hysteresis effect. However, the overall sensitivity of the magnetic response to the state-of-charge lies in the range of 0.03%, which makes practical measurement challenging. In cyclic water gas shift reactors, the sensitivity is 4 orders of magnitude higher and without phase separation, no hysteresis occurs. This shows that the method is suitable for such reactors, in which large changes of the magnetic permeability of the active material occurs.
分析了在化学或电化学反应器中,将磁化率与多孔活性物质的氧化态相关联的可能性。使用反应器的分层模型计算磁导率。该模型应用于两个实际例子:磷酸铁锂(LiFePO₄)电池,其中氧化态与充电状态相对应;循环水煤气变换反应器,其中氧化态与催化剂的消耗相对应。在磷酸铁锂电池中,正极中LiFePO₄颗粒中锂化和脱锂相的相分离会产生磁滞效应,即磁导率取决于电极的历史状态。在快速充电或放电期间,电极中锂分布不均匀会降低磁滞效应。然而,磁响应对于充电状态的整体灵敏度在0.03%的范围内,这使得实际测量具有挑战性。在循环水煤气变换反应器中,灵敏度高4个数量级且无相分离,不会出现磁滞现象。这表明该方法适用于活性材料磁导率发生较大变化的此类反应器。