面向大功率全钒液流电池的传质过程优化及低温性能改善研究

全钒液流电池作为一种新型电化学储能技术，本征安全、易规模化、寿命长，在大规模长时储能领域受到了广泛关注。目前，全钒液流电池的产业化仍然受到了高昂的建造成本及较窄的运行温度范围的限制。提升电池的功率密度及运行温度区间，被认为是推动其进一步商业化推广的有效措施。目前在实验室级别，全钒液流电池的功率密度、能量效率等关键指标已经取得了一定的突破。然而，在将电极面积放大以提升功率的过程中，会观察到明显的性能衰减。另一方面，在环境温度较低时，会出现离子迁移率降低、电解液电导率下降、化学反应动力学变缓等现象，造成电池性能明显下降，影响电池宽温域运行。如何减少电极面积放大过程中的性能衰减，以及改善电池低温性能成为了该技术商业化道路上亟需解决的问题。基于此，本文对全钒液流电池在面向大功率应用时的传质过程优化及低温性能改善方面展开了研究，并提出了相应的解决策略。具体研究内容如下：

首先，基于活性物质传输与电化学反应耦合的三维模型，以提升多孔电极表面活性物质分布均匀度为目的，提出了分层叉指流场设计。相比起传统的单流道设计，该设计显著降低了电池面积放大过程中的流场进出口的压力损失和运行过程中的浓差极化。在电流密度为250 mA·cm^-2，比流量为3 mL·min^-1·cm^-2时，基于国标（NB/T42081-2016）测试的50cm²的单电池能量效率可以达到68.61%，比传统单流道叉指流场高5.25%。

在低温性能改善方面，本课题基于原位交换机制，将引入氯离子添加剂的混酸电解液应用于低温环境，通过氯离子与钒离子的键合作用完成配体交换过程，形成络合物，这些络合物在电解液中以高动态性的溶剂化结构形式存在，有效增加了电解液中离子的活度并减小了电解液的粘度。从而极大改善了全钒液流电池的低温性能。实验表明：在温度为-10 ℃以及电流密度为150 mA·cm^-2时，电池的能量效率和电解液利用率相比于传统的硫酸电解液提高了5.08%和20.45%。

这些研究结果表明，通过分层叉指流场设计和电解液离子调控可以有效提升全钒液流电池大功率应用时的传质过程及低温性能。

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