山东大学杨剑团队以四苯基卟啉为例，报道了近单离子导电溶胶电解质对高级水性锌金属电池的自发分子聚集。相关研究成果发表在2024年3月27日出版的国际学术期刊《德国应用化学》。

金属锌作为一种很有前途的水性电池阳极，面临着枝晶生长和副反应的严峻挑战。

该文探讨了四苯基卟啉四磺酸（TPPS）作为先进锌阳极的电解质添加剂。有趣的是，TPPS自发地组装成独特的聚集体。当聚集体吸附在锌阳极上时，与报道的单个分子相比，聚集体增强了对电解质渗透和枝晶生长的抵抗力。同时，TPPS促进了Zn²⁺溶剂化鞘中的阴离子缔合，并将Zn²⁺的转移数提高到0.95。因此，阴离子相关的副反应和阴离子诱导的电极过电位相应地减少。

在这种情况下，含有TPPS的电解质表现出优异的电化学性能。即使在高负载MnO₂（25mg cm^-2）、有限的Zn供应（N/P比=1.7）和贫电解质（15uL mAh^-1）的情况下，与报道的数据相比，全电池仍然表现出更高的累积容量。这种电解质的优点也适用于其他阴极材料。在苛刻条件下，Zn||NaV₃O₈·1.5H₂O的袋状电池在0.4℃下实现约0.35 Ah的容量。

附：英文原文

Title: Spontaneous Molecule Aggregation for Nearly Single-Ion Conducting Sol Electrolyte to Advanced Aqueous Zinc Metal Batteries: The Case of Tetraphenylporphyrin

Author: Jingjing Dong, Long Su, Huili Peng, Dongdong Wang, Hanwen Zong, Gulian Wang, Jian Yang

Issue&Volume: 2024-03-27

Abstract: Zn metal as a promising anode of aqueous batteries faces the severe challenges from dendrite growth and side reactions. Here, tetraphenylporphyrin tetrasulfonic acid (TPPS) is explored as an electrolyte additive for advanced Zn anodes. It is interesting to note that TPPS spontaneously assembles into unique aggregates. As they adsorb on the Zn anode, the aggregates enhance the resistance to electrolyte percolation and dendrite growth compared to the reported single molecules. Meanwhile, TPPS facilitates anion association in the solvation sheath of Zn2+, and boosts the transference number of Zn2+ up to 0.95. Therefore, anion-related side reactions and anion-induced electrode overpotentials are reduced accordingly. In this context, the electrolyte containing TPPS exhibits the excellent electrochemical performance. Even under a high loading of MnO2 (25 mg cm-2), a limited Zn supply (N/P ratio=1.7), and a lean electrolyte (15 uL mAh-1), the full cells still represent a higher cumulative capacity compared to the reported data. The advantages of this electrolyte are also adapted to other cathode materials. The pouch cells of Zn|| NaV3O8·1.5H2O realize a capacity of ~0.35 Ah at 0.4 C under harsh conditions.

DOI: 10.1002/anie.202401441

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202401441