Model for the Particle Size, Overpotential, and Strain Dependence of Phase Transition Pathways in Storage Electrodes: Application to Nanoscale Olivines
Model for the Particle Size, Overpotential, and Strain Dependence of Phase Transition Pathways in Storage Electrodes: Application to Nanoscale Olivines
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DOI：
10.1021/cm803172s
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发表时间：
2009-03
影响因子：
8.6
通讯作者：
M. Tang;H. Huang;N. Meethong;Y. Kao;W. Carter;Y. Chiang
中科院分区：
文献类型：
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作者：
M. Tang;H. Huang;N. Meethong;Y. Kao;W. Carter;Y. Chiang
在从无线设备到电动车辆到电网稳定的应用的改进电能存储的驱动中，纳米材料作为离子存储电极越来越受到关注。基于LiMPO4（M = Fe、Mn、Co、Ni）的纳米级橄榄石是一类化合物，最近的实验发展揭示了与较大颗粒相比非常不同的相变和固溶度行为。橄榄石可能是一个范例的广义行为，亚稳结晶或非晶相的电化学反应过程中产生的大驱动力下产生的。在这里，我们使用一个扩散界面热力学模型来评估条件下，无定形相变可能发生在纳米级LiMPO4颗粒。有三个主要结论。首先，假设与类似的固体，非晶相具有较低的表面能，它被发现，最初的结晶相可能会经历非晶化循环过程中，当…
In the drive toward improved electrical energy storage for applications ranging from wireless devices to electric vehicles to grid stabilization, nanoscale materials are of growing interest as ion storage electrodes. Nanoscale olivines based on LiMPO4 (M = Fe, Mn, Co, Ni) are one class of compounds for which recent experimental developments reveal very different phase transition and solid-solubility behavior compared to larger particles. The olivines may be an exemplar for generalized behavior for which metastable crystalline or amorphous phases are produced under the large driving forces incurred during electrochemical reactions. Here we use a diffuse-interface thermodynamic model to assess the conditions under which amorphous phase transitions may occur in nanoscale LiMPO4 particles. There are three central conclusions. First, assuming as with similar solids that the amorphous phase has the lower surface energy, it is found that an initially crystalline phase may undergo amorphization during cycling whe...