Superlithiophilic Ag Particles Embedded in Flexible Polymer Solid Electrolyte Interface Films for Dendrite-Free Lithium Metal Anodes
Superlithiophilic Ag Particles Embedded in Flexible Polymer Solid Electrolyte Interface Films for Dendrite-Free Lithium Metal Anodes
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DOI：
10.1021/acssuschemeng.3c04640
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发表时间：
2023-08
期刊：
影响因子：
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通讯作者：
Weiwei Jiang;Gan Qiu;Dan Wu;Jing Zhang;Long Huang;Z. Yue;Yuanyuan Dai;Fugen Sun
中科院分区：
文献类型：
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作者：
Weiwei Jiang;Gan Qiu;Dan Wu;Jing Zhang;Long Huang;Z. Yue;Yuanyuan Dai;Fugen Sun
通过滴注AgNO 3和PVDF-HFP混合溶液在金属锂阳极表面成功构建了一种具有超亲锂性、高机械强度、快速离子导电性和自修复能力的新型协同复合膜。AgNO 3和PVDF-HFP与Li金属自发反应后，反应生成Ag、Li 3 N、LiNxOy和LiF颗粒以及未反应的Ag+离子嵌入PVDF-HFP基体中，形成Ag/PH薄膜。Ag/PH薄膜具有超亲锂Ag控制Li成核、柔性PVDF-HFP适应体积变化、离子导电Li 3 N/LiF加速Li+离子迁移和Ag+包裹自愈等协同效应，可有效诱导Li金属均匀成核/沉积，防止锂枝晶在充放电循环中的不可控生长。因此，受保护的Li金属阳极（Ag/PH@Li）表现出优异的长期循环稳定性，在对称电池中具有非常小的过电位。当与LiNi 0.8Co 0.1Mn 0.1O2阴极配对时，Ag/PH@Li阳极在0.5C、1C和2C的电流速率下循环300次后仍具有分别为150、141和128 mAh g-1的提高的可逆容量，表明它们在高能量密度锂金属二次电池中具有显著的应用潜力。
A novel synergistic composite film with multifunctional merits of superlithiophilicity, high mechanical strength, fast ionic conductivity, and self-healing capability was successfully constructed by drop casting AgNO3and PVDF-HFP mixed solution onto the metallic Li anode surfaces. After the spontaneous reaction of AgNO3and PVDF-HFP with Li metal, the reaction produced Ag, Li3N, LiNxOy, and LiF particles together with the unreacted Ag+ions embedded in the PVDF-HFP matrix, resulting in the formation of Ag/PH films. Benefitting from the synergistic effects, including the superlithiophilic Ag to control Li nucleation, flexible PVDF-HFP to adapt volume change, the ionic conductive Li3N/LiF to quicken the Li+ion transfer, and the encapsulated Ag+to self-heal cracks, the Ag/PH films could effectively induce an even nucleation/deposition of Li metal and prevent the uncontrollable growth of dendritic Li during charging/discharging cycles. Therefore, the protected Li metal anodes (Ag/PH@Li) exhibit excellent long-term cycling stability with very small overpotential in the symmetric cells. When paired with the LiNi0.8Co0.1Mn0.1O2cathodes, the Ag/PH@Li anodes still possess improved reversible capacities of 150, 141, and 128 mAh g–1, respectively, at the current rates of 0.5 C, 1 C, and 2 C after the 300th cycle, demonstrating their significant potential of application for the high-energy-density Li metal secondary batteries.