上海交通大学周永丰团队近期实现了超分子聚阴离子作为无阳极锂金属电池有效的界面层。这一研究成果发表在2025年5月13日出版的《德国应用化学》杂志上。

在过去十年中，由主客体相互作用驱动的超分子聚合物（SP）取得了长足的进步，但所涉及的客体物种主要是中性分子或阳离子。用于超分子聚合的强而可靠的大环阴离子相互作用备受追捧，但这类具有带负电荷骨架的SP的功能在很大程度上仍未得到探索。 

研究组报道了一个四脲大环与两个高亲和力有机磷阴离子之间的新型主客体相互作用（缔合常数K_a=1.06×10⁹ M^-2）。它可以作为非共价接头，有效地将低分子量聚环氧乙烷（PEO）二有机磷酸酯连接成长线性SP。作为无阳极锂（Li）金属电池中的界面层，聚合物材料通过静电吸引促进Li⁺的吸收和去溶剂化，并通过聚合物主链中交替排列的阴离子键和PEO单元实现Li⁺的快速传输。

因此，SP层使Li⁺通量均匀化，以实现均匀的Li沉积，并将LiFePO₄全电池的电化学性能显著提高了285%，循环稳定性超过200次。这些发现为具有可调结构和成分的新型阴离子SP家族铺平了道路，并表明它们在未来电池中的应用前景广阔。

附：英文原文

Title: Supramolecular Polyanions as Effective Interphase Layers for Anode-Free Lithium Metal Batteries

Author: Yongfeng Zhou, Jinghan Li, Yupo Xu, Wei You, Chengkai Hong, Shui Yu, Zhaofeng Ouyang, Zhaoming Zhang, Wei Yu, Hao Sun, Chunyang Yu, Wenfeng Jiang

Issue&Volume: 2025-05-13

Abstract: Supramolecular polymers (SPs) driven by host-guest interactions have seen considerable advancements over the past decade, but the guest species involved are predominantly neutral molecules or cations. Strong and dependable macrocycle-anion interactions for supramolecular polymerization are highly sought after, yet the functionalities of this class of SPs featuring negatively charged backbones remain largely unexplored. Here we report a novel host-guest interaction between one tetraurea macrocycle and two organophosphate anions with high affinity (association constant Ka = 1.06 × 109 M2). It can serve as noncovalent joints to efficiently link low-molecular-mass polyethylene oxide (PEO) diorganophosphates into long linear SPs. Being used as an interphase layer in anode-free lithium (Li) metal batteries, the polymer material promotes Li+ absorption and desolvation through electrostatic attractions, and enables fast Li+ transport by the alternatingly arranged anionic linkages and PEO units in the polymer main chain. As a result, the SP layer homogenizes Li+ flux to achieve uniform Li deposition, and significantly improves the electrochemical performance of LiFePO4 full batteries by a factor of 285% with cycling stability over 200 cycles. These findings pave the way for a new family of anion-based SPs with tunable architectures and compositions, and suggest their promising applications in future batteries.

DOI: 10.1002/anie.202505794

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202505794