原位聚合三维陶瓷骨架增强全固态锂电池电解质

doi:10.15541/jim20200152

摘要/Abstract

摘要：

有机/无机复合电解质被认为是全固态锂电池中最具潜力的固态电解质之一, 但由于无机填料易团聚, 通过提高无机填料含量来改善复合电解质的电导率难有成效。此外, 在全固态锂电池中, 电解质和电极之间松散的固-固接触造成过大的界面阻抗, 限制了全固态锂电池的性能。本研究采用固相法合成具有Li⁺连续传输通道的自支撑三维多孔Li_6.4Al_0.1La₃Zr_1.7Ta_0.3O₁₂骨架, 并利用原位聚合的方法构筑一体化电解质/电极固-固界面。此策略指导合成的复合电解质的室温电导率可达1.9×10^-4 S·cm^-1。同时, 一体化的界面使得Li-Li对称电池的界面阻抗从1540 Ω·cm ²降低至449 Ω·cm ², 因此4.3 V(vs. Li⁺/Li)的LiCoO₂|Li全固态锂电池展现出良好的电化学性能。

关键词: 固态复合电解质, 原位聚合, 多孔骨架, 全固态电池

Abstract:

Organic/inorganic composites have been considered as promising electrolyte candidates in all solid-state lithium batteries. Aiming at improving the conductivity significantly by increasing the frequently-used 0D or 1D ceramic nano-fillers to high content is unsuccessful due to the particle tendency to agglomeration. What's worse, the loose contact between the solid electrolyte and solid electrodes is much of a serious barrier to the performance and thus to the application of all solid-state lithium batteries. Herein, self-supported 3D porous Li_6.4Al_0.1La₃Zr_1.7Ta_0.3O₁₂ frameworks are employed to provide percolated fast Li⁺ conductive pathway while in-situ polymerization of poly(ethylene glycol) methyl ether acrylate can integrate the loose solid-solid interface and reduce the interfacial resistance efficiently. Inspiringly, the Li⁺ conductivity of the composite exhibits 1.9×10^-4 S·cm^-1 at room temperature. The interfacial resistance in Li-Li batteries decreases significantly from 1540 to 449 Ω·cm ², rendering good capacity and cyclability of the 4.3 V (vs. Li⁺/Li) LiCoO₂|Li all solid-state lithium battery.

Key words: solid composite electrolyte, in-situ polymerization, porous framework, all solid-state battery

中图分类号:

TQ174

颜一垣, 鞠江伟, 于美燕, 陈守刚, 崔光磊. 原位聚合三维陶瓷骨架增强全固态锂电池电解质[J]. 无机材料学报, 2020, 35(12): 1357-1364.

YAN Yiyuan, JU Jiangwei, YU Meiyan, CHEN Shougang, CUI Guanglei. In-situ Polymerization Integrating 3D Ceramic Framework in All Solid-state Lithium Battery[J]. Journal of Inorganic Materials, 2020, 35(12): 1357-1364.

图/表 8

图1 (a)非原位聚合策略和(b)原位聚合策略制备的ASLB内部结构示意图

Fig. 1 Schematic illustration of ASLB structure prepared via (a) ex-situ and (b) in-situ methods with p-LLZTO as ceramic fillers

图2 (a)标准LLZO及本实验制备的LLZTO粉末和p-LLZTO的XRD图谱; (b) p-LLZTO的截面SEM照片; (c)p-LLZTO的孔径分布曲线; (d)致密LLZTO和p-LLZTO的室温阻抗图谱(插图: 局部放大的致密LLZTO阻抗谱)

Fig. 2 (a) XRD patterns of standard LLZO, the as-prepared LLZTO powders and p-LLZTO; (b) Cross sectional SEM image of p-LLZTO; (c) Pore size distribution of p-LLZTO; (d) EIS plots of dense LLZTO and p-LLZTO at room temperature with inset showing the partial magnified spectrum of the dense LLZTO

图3 (a)PEGMEA、P(PEGMEA)和3D composite中P(PEGMEA)的红外图谱; (b)PEGMEA和3D composite中P(PEGMEA)的核磁共振氢谱及相关结构式(溶剂为氘代N,N-二甲基甲酰胺); (c)60 ℃条件下steel|3D composite|steel电池欧姆阻抗与加热时间关系曲线, 插图为有/无p-LLZTOP的PEGMEA在小瓶中60 ℃加热24 h后的照片; (d)P(PEGMEA)和3D composite的电导率与温度的关系曲线; (e)3D composite的截面SEM照片及元素分布图

Fig. 3 (a) FT-IR spectra of PEGMEA, P(PEGMEA), and P(PEGMEA) from the 3D composite; (b) 1H NMR spectra of PEGMEA and P(PEGMEA) from the 3D composite(the solvents are deuterated N,N-dimethylformamide) with insets showing the corresponding structural formula of PEGMEA and P(PEGMEA); (c) Thermal evolution of ohmic resistance at 60 ℃ for steel|3D composite|steel symmetrical cell with inset showing the digital image of PEGMEA with/without p-LLZTO after heat-treatment at 60 ℃ for 24 h; (d) Relation between ionic conductivity of electrolyte and temperature for P(PEGMEA) and 3D composite; (e) Cross sectional SEM image and element mapping analysis of the 3D composite

表1 不同固态电解质的室温电导率$(\sigma_{Li^+})$

Table 1 Conductivities $(\sigma_{Li^+})$ of different solid electrolytes at room temperature

Electrolyte	Lithium salt	EO^a : Li⁺	Conductivity of polymer/(S·cm^-1)	Conductivity of composite/(S·cm^-1)	Promotion factor	Ref.
PEO/LATP particles	LiClO₄	15 : 1	1.3×10^-6	9.5×10^-6	7.5	[25]
PEO/LLZO fibers	LiTFSI^b	-	2.5×10^-6	2.7×10^-5	11	[26]
PEO/LATP^c fibers	LiTFSI	8 : 1	3.2×10^-6	4.9×10^-5	15	[27]
PEO/3D LLZO	LiTFSI	10 : 1	1.8×10^-6	8.5×10^-5	47	[19]
PEO/3D LLTO^d	LiTFSI	10 : 1	2.2×10^-6	8.8×10^-5	40	[18]

图S1 3D composite室温下的线性扫描伏安曲线

Fig. S1 Linear sweep voltammetry measurement for 3D composite at room temperature

图S2 (a) Li|P(PEGMEA)|Li和(b)Li|3D composite|Li电池室温下极化过程电流随时间变化曲线

Fig. S2 Current variation with time during polarization of (a) Li|P(PEGMEA)|Li and (b) Li|3D composite|Li symmetrical cell at room temperature

图4 热处理(a~c)前(d~f)后基于(a, d)PEGMEA、(b, e)LLZTO和(c, f)3D composite的Li-Li对称电池的EIS图谱; 基于不同电解质的Li-Li电池处理前后(g)欧姆阻抗和(h)界面阻抗对比; (i)P(PEGMEA)和3D composite的Li-Li电池室温下的直流恒流循环曲线(上插图为LLZTO的Li-Li电池室温下的直流恒流循环曲线, 下插图为3D composite的Li-Li电池的局部放大极化曲线, 电流密度为0.1 mA·cm-2)

Fig. 4 EIS plots of (a-c) pre- and (d-f) post-treated Li-Li symmetrical batteries based on (a, d) PEGMEA, (b, e) LLZTO, (c, f) 3D composites; (g) Ohmic and (h) interfacial resistance comparison of pre- and post-treated Li-Li symmetrical cells; (i) DC galvanostatic cycle of Li-Li symmetrical batteries based on P(PEGMEA) and the 3D composite under room temperature at 0.1 mA·cm-2 with insets showing D.C. galvanostatic cycle of Li-Li symmetrical battery based on LLZTO(up) and the magnified profile of Li|3D composite|Li(down)

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