Lead-acid batteries fail faster in partial state-of-charge start-stop technology than in SLI application. Accumulation of lead sulfate on negative electrode's surface has been identified as the cause. It is also known that life can be enhanced by increasing capacitance of negative electrode. A bench-marking test cycle is used to explain these observations through a one-dimensional model. It is shown that, at the large discharge current densities used, faradaic reactions in the electrodes are spatially inhomogeneous, and charging is unable to reverse its effects. Consequently, lead sulfate deposit is larger on electrode's surface than at its center. Model uses a rate expression for charging modified to include diffusion of Pb2+, and predicts that sulfate continues to accumulate with cycling. A portion of electrode becomes inactive when volume fraction of sulfate reaches a critical value there. Battery fails when inactive area becomes large. It is shown that double-layer capacitance suppresses the non-uniformity in the faradaic reaction and alters the pattern of accumulation of sulfate. Negative electrode does not benefit from this since its capacitance is low. Sulfate accumulates in positive electrode also, but does not reach critical levels since positive electrode's capacitance is large. This explains the life enhancing effect of capacitance. (C) The Author(s) 2017. Published by ECS. All rights reserved.

中文翻译：

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HRPSoC 应用中双层电容和铅酸电池失效的影响建模

铅酸电池在部分充电状态启停技术中的失效速度比在 SLI 应用中更快。硫酸铅在负极表面的积累已被确定为原因。还已知通过增加负极的电容可以提高寿命。基准测试循环用于通过一维模型解释这些观察结果。结果表明，在使用大放电电流密度时，电极中的法拉第反应在空间上是不均匀的，充电无法逆转其影响。因此，电极表面的硫酸铅沉积物大于其中心。模型使用修改后的充电速率表达式以包括 Pb2+ 的扩散，并预测硫酸盐随着循环继续积累。当硫酸盐的体积分数达到临界值时，电极的一部分变得不活跃。当非活动区域变大时电池失效。结果表明，双层电容抑制了法拉第反应的不均匀性并改变了硫酸盐的积累模式。负电极不会从中受益，因为它的电容很低。硫酸盐也会积聚在正极中，但由于正极的电容很大，因此不会达到临界水平。这解释了电容的寿命增强效果。(C) 作者 2017。ECS 出版。版权所有。结果表明，双层电容抑制了法拉第反应的不均匀性并改变了硫酸盐的积累模式。负电极不会从中受益，因为它的电容很低。硫酸盐也会积聚在正极中，但由于正极的电容很大，因此不会达到临界水平。这解释了电容的寿命增强效果。(C) 作者 2017。ECS 出版。版权所有。结果表明，双层电容抑制了法拉第反应的不均匀性并改变了硫酸盐的积累模式。负电极不会从中受益，因为它的电容很低。硫酸盐也会积聚在正极中，但由于正极的电容很大，因此不会达到临界水平。这解释了电容的寿命增强效果。(C) 作者 2017。ECS 出版。版权所有。