ZIF-8复合PEO基固态电解质的制备与改性研究

doi:10.19799/j.cnki.2095-4239.2022.0532

摘要/Abstract

摘要：

在聚环氧乙烷(PEO)基固体聚合物电解质中加入无机填料，是一种低成本、有效改善其力学和电化学性能的方法。为了更有效地改善PEO基固态电解质的电化学性能，本工作采用流延法制备了纳米沸石咪唑骨架材料(ZIF-8)与聚氧化乙烯(PEO)复合的固态电解质。通过扫描电子显微镜(SEM)、X射线衍射(XRD)等物理表征和电化学阻抗谱(EIS)、伏安线性扫描(LSV)、充放电循环等电化学测试手段，证明了加入20%ZIF-8纳米粒子的PEO基复合固态电解质CPE20具有最小的体电阻、较宽的电化学稳定窗口与最低的活化能(8.4×10^-3 eV)；20 ℃时，其电导率达到了4.9×10^-5 S/cm(比纯PEO高一个数量级)；70 ℃时，其电导率为1.08×10^-3 S/cm(与液态电解液相当)；CPE20的锂离子迁移数提高至0.46，而纯PEO基固态电解质为0.36；采用CPE20制备的LiFePO₄||Li电池在室温下具有良好的容量和循环性能，而且容量保持率超过96%。加入适量的惰性填料ZIF-8时，可以有效降低聚合物的结晶度，增加聚合物的非晶区，促进锂盐的溶解，提高锂离子的迁移率，使复合固态电解质具有更加优异的电化学性能。因此添加ZIF-8的PEO基固相聚合物在固态金属锂电池中具有广阔的应用前景。

关键词: 电化学储能, 电解质, 聚氧化乙烯, 沸石咪唑骨架材料

Abstract:

Incorporating inorganic fillers into polyethylene oxide (PEO)-based solid polymer electrolytes is a low-cost and effective method to improve their mechanical and electrochemical properties. The solid electrolyte composite of zeolite imidazole skeleton material (ZIF-8) and PEO was prepared using flow-casting method to effectively improve the electrochemical performance of the PEO solid electrolyte. Physical characterizations of scanning electron microscopy, X-ray diffraction, and electrochemical measurement methods, such as electrochemical impedance spectroscopy, linear sweep voltammetry, and charge-discharge cycle, proved that the PEO-based composite solid electrolyte CPE20 with 20%ZIF-8 nanoparticles had the lowest resistance, a broader electrochemical stability window, and an activation energy of 8.4×10^-3 eV. At 20 ℃, the conductivity of CPE20 reached 4.9×10^-5 S/cm, which is one order of magnitude higher than that of pure PEO. When the temperature was increased to 70 ℃, the conductivity reached 1.08×10^-3 S/cm. The number of lithium-ion transference of CPE20 increased to 0.46, while that of pure PEO solid electrolyte is 0.36. Thus, the CPE20 preparation of LiFePO₄||Li battery has good capacity and cycle performance at room temperature, with a capacity rate of more than 96%. Therefore, adding an appropriate amount of ZIF-8 inert filler can effectively reduce the crystallinity and increase the amorphous zone of the polymer. It can also promote the dissolution of lithium salts and improve the mobility of lithium ions, which make the composite solid electrolyte has more excellent electrochemical performance. Thus, the findings show that the PEO-based solid polymer electrolytes with ZIF-8 have potential application in solid-state lithium batteries.

Key words: chemical energy storage, electrolytes, polyvinyl oxide, zeolite imidazole skeleton material

中图分类号:

TQ 152

黄渭彬, 张彪, 范金成, 杨伟, 邹汉波, 陈胜洲. ZIF-8复合PEO基固态电解质的制备与改性研究[J]. 储能科学与技术, 2023, 12(4): 1083-1092.

Weibin HUANG, Biao ZHANG, Jincheng FAN, Wei YANG, Hanbo ZOU, Shengzhou CHEN. Preparation and modification of ZIF-8 composite PEO based solid electrolyte[J]. Energy Storage Science and Technology, 2023, 12(4): 1083-1092.

图/表 14

图1

图2

图3

图4

图5

图6

图 7

图8

表1

图 9

图 10

图 11

表 2

CPE0和CPE20恒流极化参数和结果"

固态电解质	I₀/μA	I_ss/μA	R₀/Ω	R_ss/Ω	ΔV/mV	$t L i +$
CPE0	0.338	0.129	262.9	267.7	10	0.36
CPE20	3.07	1.44	86.7	90.1	10	0.46

表 2

图 12

参考文献 32

1	WANG M Q, LIU X L, QIN B Y, et al. In-situ etching and ion exchange induced 2D-2D MXene@Co₉S₈/CoMo₂S₄ heterostructure for superior Na⁺ storage[J]. Chemical Engineering Journal, 2023, 451: doi: 10.1016/j.cej.2022.138508.
2	CHEN W, CHEN J L, DENG J Y, et al. Improvement of cycling stability of Li_1.2Mn_0.54Co_0.13Ni_0.13O₂microrods cathode material modified with in situ polymerization of aniline in HTFSI solution[J]. International Journal of Energy Research, 2022, 46(15): 22960-22970.
3	周伟东, 黄秋, 谢晓新, 等. 固态锂电池聚合物电解质研究进展[J]. 储能科学与技术, 2022, 11(6): 1788-1805.
	ZHOU W D, HUANG Q, XIE X X, et al. Research progress of polymer electrolyte for solid state lithium batteries[J]. Energy Storage Science and Technology, 2022, 11(6): 1788-1805.
4	WU Y X, LI Y, WANG Y, et al. Advances and prospects of PVDF based polymer electrolytes[J]. Journal of Energy Chemistry, 2022, 64: 62-84.
5	CHENG X B, ZHANG R, ZHAO C Z, et al. A review of solid electrolyte interphases on lithium metal anode[J]. Advanced Science (Weinheim, Baden-Wurttemberg, Germany), 2015, 3(3): doi: 10.1002/advs.201500213.
6	DU Z Z, AI W, YANG J, et al. In situ fabrication of Ni₂P nanoparticles embedded in nitrogen and phosphorus codoped carbon nanofibers as a superior anode for Li-ion batteries[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(11): 14795-14801.
7	汤匀, 岳芳, 郭楷模, 等. 全固态锂电池技术发展趋势与创新能力分析[J]. 储能科学与技术, 2022, 11(1): 359-369.
	TANG Y, YUE F, GUO K M, et al. Analysis of the development trend and the innovation ability of an all-solid-state lithium battery technology[J]. Energy Storage Science and Technology, 2022, 11(1): 359-369.
8	GUAN P Y, ZHOU L, YU Z L, et al. Recent progress of surface coating on cathode materials for high-performance lithium-ion batteries[J]. Journal of Energy Chemistry, 2020, 43: 220-235.
9	JI X Q, XIA Q, XU Y X, et al. A review on progress of lithium-rich Manganese-based cathodes for lithium ion batteries[J]. Journal of Power Sources, 2021, 487: doi:10.1016/j.jpowsour.2020.229362.
10	MANTHIRAM A. A reflection on lithium-ion battery cathode chemistry[J]. Nature Communications, 2020, 11(1): 1-9.
11	BORAH S, GUHA A K, SAIKIA L, et al. Nanofiber induced enhancement of electrical and electrochemical properties in polymer gel electrolytes for application in energy storage devices[J]. Journal of Alloys and Compounds, 2021, 886: doi:10.1016/j.jallcom.2021.161173
12	许卓, 郑莉莉, 陈兵, 等. 固态电池复合电解质研究综述[J]. 储能科学与技术, 2021, 10(6): 2117-2126.
	XU Z, ZHENG L L, CHEN B, et al. Overview of research on composite electrolytes for solid-state batteries[J]. Energy Storage Science and Technology, 2021, 10(6): 2117-2126.
13	ZHANG H, OTEO U, ZHU H J, et al. Enhanced lithium-ion conductivity of polymer electrolytes by selective introduction of hydrogen into the anion[J]. Angewandte Chemie (International Ed in English), 2019, 58(23): 7829-7834.
14	ZHAO Q, STALIN S, ZHAO C Z, et al. Designing solid-state electrolytes for safe, energy-dense batteries[J]. Nature Reviews Materials, 2020, 5(3): 229-252.
15	ZHANG Z, YINGHUANG, ZHANG G Z, et al. Three-dimensional fiber network reinforced polymer electrolyte for dendrite-free all-solid-state lithium metal batteries[J]. Energy Storage Materials, 2021, 41: 631-641.
16	刘当玲, 王诗敏, 高智慧, 等. 三维NZSPO/PAN-[PEO-NaTFST]复合钠离子电池固体电解质[J]. 储能科学与技术, 2021, 10(3): 931-937.
	LIU D L, WANG S M, GAO Z H, et al. Properties of three-dimensional NZSPO/PAN-[PEO-NATFST]sodium-battery-composite solid electrolyte[J]. Energy Storage Science and Technology, 2021, 10(3): 931-937.
17	XU L, WEI K Y, CAO Y, et al. The synergistic effect of the PEO-PVA-PESf composite polymer electrolyte for all-solid-state lithium-ion batteries[J]. RSC Advances, 2020, 10(9): 5462-5467.
18	CHEN H, ZHOU C J, DONG X R, et al. Revealing the superiority of fast ion conductor in composite electrolyte for dendrite-free lithium-metal batteries[J]. ACS Applied Materials & Interfaces, 2021, 13(19): 22978-22986.
19	FAN L Z, NAN C W, ZHAO S J. Effect of modified SiO₂ on the properties of PEO-based polymer electrolytes[J]. Solid State Ionics, 2003, 164(1/2): 81-86.
20	ROSENWINKEL M P, ANDERSSON R, MINDEMARK J, et al. Coordination effects in polymer electrolytes: Fast Li⁺ transport by weak ion binding[J]. The Journal of Physical Chemistry C, 2020, 124(43): 23588-23596.
21	SHENG O W, JIN C B, LUO J M, et al. Mg₂B₂O₅ nanowire enabled multifunctional solid-state electrolytes with high ionic conductivity, excellent mechanical properties, and flame-retardant performance[J]. Nano Letters, 2018, 18(5): 3104-3112.
22	张林森, 王士奇, 王利霞, 等. PEO基Li⁺-g-C₃N₄复合固态电解质的制备及其电化学性能[J]. 储能科学与技术, 2022, 11(11): 3463-3469.
	ZHANG L S, WANG S Q, WANG L X, et al. Synthesis and performances of Li⁺ modified g-C₃N₄ for PEO-based composite solid electrolyte[J]. Energy Storage Science and Technology, 2022, 11(11): 3463-3469.
23	LI X L, YANG L, SHAO D S, et al. Preparation and application of poly (ethylene oxide)-based all solid-state electrolyte with a walnut-like SiO₂ as nano-fillers[J]. Journal of Applied Polymer Science, 2020, 137(24): 48810.
24	LIANG F Q, WEN Z Y. MOF/poly(ethylene oxide) composite polymer electrolyte for solid-state lithium battery[J]. Journal of Inorganic Materials, 2021, 36(3): 332.
25	QI Z Y, PEI Y C, GOH T W, et al. Conversion of confined metal@ZIF-8 structures to intermetallic nanoparticles supported on nitrogen-doped carbon for electrocatalysis[J]. Nano Research, 2018, 11(6): 3469-3479.
26	YANG X B, WEN Z D, WU Z L, et al. Synthesis of ZnO/ZIF-8 hybrid photocatalysts derived from ZIF-8 with enhanced photocatalytic activity[J]. Inorganic Chemistry Frontiers, 2018, 5(3): 687-693.
27	TRAN U P N, LE K K A, PHAN N T S. Expanding applications of metal-organic frameworks: Zeolite imidazolate framework ZIF-8 as an efficient heterogeneous catalyst for the Knoevenagel reaction[J]. ACS Catalysis, 2011, 1(2): 120-127.
28	CHIZALLET C, LAZARE S, BAZER-BACHI D, et al. Catalysis of transesterification by a nonfunctionalized metal-organic framework: Acido-basicity at the external surface of ZIF-8 probed by FTIR and ab initio calculations[J]. Journal of the American Chemical Society, 2010, 132(35): 12365-12377.
29	XI J Y, QIU X P, CUI M Z, et al. Enhanced electrochemical properties of PEO-based composite polymer electrolyte with shape-selective molecular sieves[J]. Journal of Power Sources, 2006, 156(2): 581-588.
30	SUN C, ZHANG J H, YUAN X F, et al. ZIF-8-based quasi-solid-state electrolyte for lithium batteries[J]. ACS Applied Materials & Interfaces, 2019, 11(50): 46671-46677.
31	KASNERYK V, POSCHMANN M P M, SERDECHNOVA M, et al. Formation and structure of ZIF-8@PEO coating on the surface of zinc[J]. Surface and Coatings Technology, 2022, 445: doi:10.1016/j.surfcoat.2022.128733.
32	JAYATHILAKA P A R D, DISSANAYAKE M A K L, ALBINSSON I, et al. Effect of nano-porous Al₂O₃ on thermal, dielectric and transport properties of the (PEO)₉LiTFSI polymer electrolyte system[J]. Electrochimica Acta, 2002, 47(20): 3257-3268.

项目	CPEO	CPE5	CPE10	CPE15	CPE20	CPE25
R_d/Ω	18.1	10.6	10.1	7.6	6.7	13.2
电导率 /(×10^-4 S/cm)	2.72	4.76	5.15	7.04	8.21	4.34
厚度/μm	94	97	100	102	104	109
E_a /(×10^-4 eV）	1.14	1.10	1.05	0.96	0.84	1.07

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