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用于无阳极锂金属电池的质子化聚苯胺修饰铜集流体

Protonated Polyaniline-Modified Copper Current Collector for Anode-Free Lithium Metal Battery.

作者信息

Li Nanrui, Kang Guohuang, Huang Shifei, Biao Jie, Liu Yanru, Kang Feiyu, Cao Yidan

机构信息

Shenzhen Geim Graphene Center, Institute of Materials Research, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055, China.

出版信息

ACS Appl Mater Interfaces. 2025 Jun 25;17(25):36627-36638. doi: 10.1021/acsami.5c04173. Epub 2025 Jun 10.

Abstract

The formation of Li dendrites and dead Li, which causes short circuits, continuous side reactions, low Coulombic efficiency (CE), and thermal runaway, significantly hinders the development of anode-free lithium metal batteries (AFLMBs). This study proposes a simple and effective method to construct an HCl-doped polyaniline modification layer on Cu foil (HPC) through chemical polymerization. The polyaniline modification layer exhibits a stable structure and good electrical conductivity after HCl doping, where the protonated and doped imide structure shows excellent lithiophilicity during cycling, promoting uniform Li deposition as a Li ion redistributor. This approach effectively suppresses dendrite growth, enhances the stability of the solid-state interphase at the anode, and extends cell cycle life. As a result, the anode-free half-cell with HPC current collector exhibits reduced overpotential of 20.6 mV and prolonged cycling life over 150 cycles at an areal capacity of 1 mA h cm and a plating/stripping rate of 1.2 mA cm/2 mA cm. Capacity retention of 63.81% and 74.01% is achieved after 100 cycles in the anode-free (/ = 0) and anode-less (/ = 1.6) full cells, respectively. This work creatively introduces a conductive polymer into the AFLMB system, enhancing our understanding of Li plating-stripping regulation strategies and offering new insights into the development of AFLMBs.

摘要

锂枝晶和死锂的形成会导致短路、持续的副反应、低库仑效率(CE)和热失控,严重阻碍了无阳极锂金属电池(AFLMBs)的发展。本研究提出了一种简单有效的方法,通过化学聚合在铜箔(HPC)上构建HCl掺杂的聚苯胺改性层。聚苯胺改性层在HCl掺杂后表现出稳定的结构和良好的导电性,其中质子化和掺杂的亚胺结构在循环过程中表现出优异的亲锂性,作为锂离子再分配器促进锂的均匀沉积。这种方法有效地抑制了枝晶生长,增强了阳极固态界面的稳定性,并延长了电池循环寿命。结果,具有HPC集流体的无阳极半电池在面积容量为1 mA h cm且电镀/剥离速率为1.2 mA cm/2 mA cm时,过电位降低了20.6 mV,循环寿命延长至150次以上。在无阳极(/ = 0)和无阳极(/ = 1.6)全电池中分别循环100次后,容量保持率分别达到63.81%和74.01%。这项工作创造性地将导电聚合物引入AFLMB系统,加深了我们对锂电镀-剥离调控策略的理解,并为AFLMBs的发展提供了新的见解。

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