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Silver Vanadium Diphosphate Ag2VP2O8: Electrochemistry and Characterization of Reduced Material providing Mechanistic Insights

机译：银磷酸二钒银Ag2VP2O8：还原材料的电化学和表征提供了机械学的见解

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摘要

Silver vanadium phosphorous oxides (AgwVxPyOz) are notable battery cathode materials due to their high energy density and demonstrated ability to form in-situ Ag metal nanostructured electrically conductive networks within the cathode. While analogous silver vanadium diphosphate materials have been prepared, electrochemical evaluations of these diphosphate based materials have been limited. We report here the first electrochemical study of a silver vanadium diphosphate, Ag2VP2O8, where the structural differences associated with phosphorous oxides versus diphosphates profoundly affect the associated electrochemistry. Reminiscent of Ag2VO2PO4 reduction, in-situ formation of silver metal nanoparticles was observed with reduction of Ag2VP2O8. However, counter to Ag2VO2PO4 reduction, Ag2VP2O8 demonstrates a significant decrease in conductivity upon continued electrochemical reduction. Structural analysis contrasting the crystallography of the parent Ag2VP2O8 with that of the proposed Li2VP2O8 reduction product is employed to gain insight into the observed electrochemical reduction behavior, where the structural rigidity associated with the diphosphate anion may be associated with the observed particle fracturing upon deep electrochemical reduction. Further, the diphosphate anion structure may be associated with the high thermal stability of the partially reduced Ag2VP2O8 materials, which bodes well for enhanced safety of batteries incorporating this material.
机译：银钒磷氧化物（AgwVxPyOz）由于其高能量密度和在阴极内形成原位Ag金属纳米结构导电网络的能力而成为电池正极材料。尽管已经制备了类似的二磷酸银钒钒材料，但是这些基于二磷酸盐的材料的电化学评估受到限制。我们在这里报告了银磷酸盐二磷酸银Ag2VP2O8的首次电化学研究，其中与磷氧化物和二磷酸盐相关的结构差异深刻地影响了相关的电化学。令人联想到Ag2VO2PO4的还原，观察到Ag2VP2O8还原后原位形成了金属银纳米颗粒。然而，与Ag2VO2PO4还原相反，Ag 2 VP 2 O 8 在继续进行电化学还原后显示出电导率显着降低。结构分析对比了母体Ag 2 VP 2 O 8 与拟议的Li 2 VP的晶体学 2 O 8 还原产物用于深入观察所观察到的电化学还原行为，其中与二磷酸根阴离子相关的结构刚度可能与所观察到的深部颗粒破裂有关电化学还原。此外，二磷酸根阴离子结构可能与部分还原的Ag 2 VP 2 O 8 材料的高热稳定性有关，这预示着良好的预兆。增强使用这种材料的电池的安全性。

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