摘要
NASICON基固态电解质(Na_(3)Zr_(2)Si_(2)PO_(12), NZSP),凭借高离子电导率、优异的化学稳定性以及宽电化学窗口等优点,被认为是下一代高能量密度固态钠离子电池具有竞争力的电解质材料。然而,NZSP电解质与钠负极间的刚性界面接触不良,会导致界面电阻增大,引起不均匀的Na沉积/剥离。为此,本工作制备了共价三嗪框架(CTF),并将其用作NZSP电解质的界面修饰层。CTF材料具有良好的电子绝缘特性,可以有效避免电子穿过电解质引起电池内部短路,并且因其软界面接触能够有效降低界面阻抗。密度泛函理论计算表明,CTF修饰层表面的负电性位点能够促进Na+的迁移,并引导Na均匀沉积/剥离,从而有效抑制电解质内部Na枝晶的生长。结果表明,经过修饰后的钠对称电池的临界电流密度提升至0.5 mA/cm^(2),在0.1 mA/cm^(2)电流密度下实现了200 h的稳定循环,组装的Na||Na_(3)V_(2)(PO_(4))_(3)/C表现出更好的倍率性能和长期循环稳定性能。本研究通过在NZSP电解质表面引入CTF修饰层,有效改善了电极/电解质界面稳定性,为构建高性能固态钠离子电池提供了有效的界面工程策略。
NASICON-type solid electrolyte Na_(3)Zr_(2)Si_(2)PO_(12)(NZSP)is a promising candidate for high-energy-density solid-state sodium-ion batteries due to its high ionic conductivity,excellent chemical stability,and wide electrochemical window.However,the rigid interface between NZSP and the sodium anode often results in elevated interfacial resistance and uneven Na deposition/stripping.To address this challenge,a covalent triazine framework(CTF)was prepared and applied as an interfacial modification layer on NZSP.The CTF exhibits strong electron-insulating properties,preventing electron leakage that could trigger internal short circuits,while its soft interfacial nature reduces impedance.Density functional theory calculations indicate that electronegative sites on the CTF surface facilitate Na+migration and promote uniform Na deposition/stripping,effectively suppressing Na dendrite formation within the electrolyte.Experimental results show that the critical current density of the modified sodium symmetric cell increases to 0.5 mA/cm^(2),enabling stable cycling for 200 h at 0.1 mA/cm^(2).The assembled Na||Na_(3)V_(2)(PO_(4))_(3)/C cell demonstrates enhanced rate capability and long-term cycling stability.Introducing a CTF modification layer on the NZSP electrolyte surface effectively stabilizes the electrode/electrolyte interface,offering a practical interface engineering strategy for high-performance solid-state sodium metal batteries.
作者
李子琛
孙钰婷
张化璞
张梦迪
闫迎春
张维民
孟秀霞
杨乃涛
LI Zichen;SUN Yuting;ZHANG Huapu;ZHANG Mengdi;YAN Yingchun;ZHANG Weimin;MENG Xiuxia;YANG Naitao(School of Chemical Engineering,Shandong University of Technology,Zibo 255000,Shandong,China)
出处
《储能科学与技术》
北大核心
2025年第12期4441-4449,共9页
Energy Storage Science and Technology
基金
国家自然科学基金(21978157,21776175)
山东省自然科学基金(ZR2022QB147,ZR2023MB093)。
关键词
钠离子电池
固态电解质
共价三嗪框架
NASICON
界面修饰
sodium-ion batteries
solid-state electrolytes
covalent triazine framework
NASICON
interface retouching
