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A Kinetics and Equilibrium Study of Vanadium Dissolution from Vanadium Oxides and Phosphates in Battery Electrolytes: Possible Impacts on ICD Battery Performance

机译：从电池电解液中的钒氧化物和磷酸盐中溶解钒的动力学和平衡研究：对ICD电池性能的可能影响

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摘要

Silver vanadium oxide (Ag2V4O11, SVO) has enjoyed widespread commercial success over the past 30 years as a cathode material for implantable cardiac defibrillator (ICD) batteries. Recently, silver vanadium phosphorous oxide (Ag2VO2PO4, SVPO) has been studied as possibly combining the desirable thermal stability aspects of LiFePO4 with the electrical conductivity of SVO. Further, due to the noted insoluble nature of most phosphate salts, a lower material solubility of SVPO relative to SVO is anticipated. Thus, the first vanadium dissolution studies of SVPO in battery electrolyte solutions are described herein. The equilibrium solubility of SVPO was ~5 times less than SVO, with a rate constant of dissolution ~3.5 times less than that of SVO. The vanadium dissolution in SVO and SVPO can be adequately described with a diffusion layer model, as supported by the Noyes-Whitney equation. Cells prepared with vanadium-treated anodes displayed higher AC impedance and DC resistance relative to control anodes. These data support the premise that SVPO cells are likely to exhibit reduced cathode solubility and thus less affected by increased cell resistance due to cathode solubility compared to SVO based cells.
机译：在过去的30年中，氧化钒银（Ag2V4O11，SVO）作为植入式心脏除颤器（ICD）电池的阴极材料已获得了广泛的商业成功。最近，银钒磷氧化物（Ag2VO2PO4，SVPO）已被研究为可能将LiFePO4的理想热稳定性方面与SVO的电导率相结合。此外，由于大多数磷酸盐的不溶性，预计SVPO相对于SVO的材料溶解度较低。因此，本文描述了SVPO在电池电解质溶液中的首次钒溶解研究。 SVPO的平衡溶解度比SVO小约5倍，溶出速率常数比SVO小约3.5倍。如Noyes-Whitney方程所支持的，可以用扩散层模型充分描述SVO和SVPO中的钒溶解度。与对照阳极相比，用钒处理过的阳极制备的电池显示出更高的交流阻抗和直流电阻。这些数据支持这样的前提，即与基于SVO的电池相比，SVPO电池可能表现出降低的阴极溶解度，因此受阴极溶解度的影响，不受电池电阻增加的影响。

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