固态锂电池用MOF/聚氧化乙烯复合聚合物电解质

doi:10.15541/jim20200206

无机材料学报 ›› 2021, Vol. 36 ›› Issue (3): 332-336.DOI: 10.15541/jim20200206 CSTR: 32189.14.10.15541/jim20200206

所属专题：能源材料论文精选(2021)；【能源环境】金属有机框架材料(202309)

• 研究快报 • 上一篇

固态锂电池用MOF/聚氧化乙烯复合聚合物电解质

梁凤青¹^,²(), 温兆银¹^,²()

1. 中国科学院上海硅酸盐研究所, 中国科学院能量转换材料重点实验室, 上海 200050
2. 中国科学院大学材料科学与光电工程中心, 北京 100049

收稿日期:2020-04-20 修回日期:2020-05-05 出版日期:2021-03-20 网络出版日期:2020-05-20
通讯作者: 温兆银, 研究员. E-mail: zywen@mail.sic.ac.cn
作者简介:梁凤青(1994-), 女, 硕士研究生. E-mail: liangfengqing@student.sic.ac.cn

MOF/Poly(Ethylene Oxide) Composite Polymer Electrolyte for Solid-state Lithium Battery

LIANG Fengqing¹^,²(), WEN Zhaoyin¹^,²()

1. CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2020-04-20 Revised:2020-05-05 Published:2021-03-20 Online:2020-05-20
Contact: WEN Zhaoyin, professor. E-mail: zywen@mail.sic.ac.cn
About author:LIANG Fengqing(1994-), female, Master candidate. E-mail: liangfengqing@student.sic.ac.cn
Supported by:
National Key R&D Program of China(2018YFB0905400);National Natural Science Foundation of China(51772315);Science and Technology Commission of Shanghai Municipality(18DZ2280800)

摘要/Abstract

摘要：

固态聚合物电解质具有柔韧性好和易于加工的优势, 可制备各种形状的固态锂电池, 杜绝漏液问题。但固态聚合物电解质存在离子电导率低以及对锂金属负极不稳定等问题。本研究以纳米金属-有机框架材料UiO-66为聚合物电解质的填料, 用于改善电解质的性能。UiO-66与聚氧化乙烯(poly(ethylene oxide), PEO)链上醚基的氧原子的配位作用以及与锂盐中阴离子的相互作用, 可显著提高聚合物电解质的离子电导率(25 ℃, 3.0×10 ^-5S/cm; 60 ℃, 5.8×10 ^-4 S/cm), 并将锂离子迁移数提高至0.36, 电化学窗口拓宽至4.9 V。此外, 制备的PEO基固态电解质对金属锂具有良好的稳定性, 对称电池在60 ℃、0.15 mA·cm ^-2电流密度下可稳定循环1000 h, 锂电池的电化学性能得到显著改善。

关键词: 复合电解质, 聚氧化乙烯, 金属-有机框架材料, 锂金属电池

Abstract:

Solid polymer electrolytes (SPEs) with high flexibility and processability enable the fabrication of leak-free solid-state batteries with varied geometries. However, SPEs usually suffer from low ionic conductivity and poor stability with lithium metal anodes. Here, we propose nano-sized metal-organic framework (MOF) material(UiO-66) as filler for poly(ethylene oxide) (PEO) polymer electrolyte. The coordination of UiO-66 with oxygen in PEO chain and the interaction between UiO-66 and lithium salt significantly improve the ionic conductivity (3.0×10 ^-5 S/cm at 25 ℃, 5.8×10 ^-4 S/cm at 60 ℃) and transference number of Li ⁺ (0.36), widen the electrochemical window to 4.9 V (vs Li ⁺/Li), enhance the stability with lithium metal anode. As a result, the as-prepared Li symmetrical cells can continuously operate for 1000 h at 0.15 mA?cm ^-2, 60 ℃. The results show that UiO-66 filler is effective to improve the electrochemical performance of polymer electrolyte.

Key words: composite electrolyte, poly(ethylene oxide), metal-organic framework material, lithium metal battery

中图分类号:

TQ174

梁凤青, 温兆银. 固态锂电池用MOF/聚氧化乙烯复合聚合物电解质[J]. 无机材料学报, 2021, 36(3): 332-336.

LIANG Fengqing, WEN Zhaoyin. MOF/Poly(Ethylene Oxide) Composite Polymer Electrolyte for Solid-state Lithium Battery[J]. Journal of Inorganic Materials, 2021, 36(3): 332-336.

图/表 3

Fig. 1 (a) Crystal structure of UiO-66, and SEM images of (b) nano-sized UiO-66 and (c) UiO-66/PEO composite polymer electrolyte

Fig. 2 (a) XRD patterns of simulated UiO-66, synthesized nano-sized UiO-66, PEO, and CPE-10%; (b) Arrhenius plots for the ionic conductivities of PEO electrolytes with different contents of UiO-66; (c) Nyqiust plots within frequency of 1 Hz-1 MHz for the CPE-10% at the temperature from 25 to 80 ℃; (d) LSV curves of SPE and CPE in SS/electrolyte/Li cells at 60 ℃; (e) DC polarization profile of symmetric Li/SPE /Li cell at an applied voltage of 10 mV at 60 ℃; (f) DC polarization profile of symmetric Li/CPE-10%/Li cell at an applied voltage of 10 mV at 60 ℃. Insets in (e,f): AC impedance spectra of the corresponding symmetric cells before and after DC polarization

Fig. 3 (a) Galvanostatic cycles with a constant current density of 0.15 mA?cm-2 for symmetric Li/CPE-10%/Li and Li/SPE/Li cells at 60 ℃, (b) magnification of galvanostatic cycles of Li/CPE-10%/Li and Li/SPE/Li cells at 1-10 cycle, and (c) magnification of galvanostatic cycles of Li/CPE-10%/Li cell at 895-900 cycle

参考文献 19

[1]	CROCE F, APPETECCHI G B, PERSI L, et al. Nanocomposite polymer electrolytes for lithium batteries. Nature, 1998,394(6692):456-458. DOI URL
[2]	CLERICUZIO M, PARKER W O, SOPRANI M, et al. Ionic diffusivity and conductivity of plasticized polymer electrolytes: PMFG-NMR and complex impedance studies. Solid State Ionics, 1995,82(3/4):179-192.
[3]	GORECKI W, ANDREANI C, BERTHIER C. NMR, DSC, conductivity study of a poly(ethylene oxide) complex electrolyte: PEO(LiClO₄)_x. Solid State Ionics, 1986,18(19):295-299.
[4]	PUTHIRATH A B, PATRA S, PAL S, et al. Transparent flexible lithium ion conducting solid polymer electrolyte. Journal of Materials Chemistry A, 2017,5(22):11152-11162.
[5]	ZHANG D, ZHANG L, YANG K, et al. Superior blends solid polymer electrolyte with integrated hierarchical architectures for all-solid-state lithium-ion batteries. ACS Appl. Mater. Inter., 2017,9(42):36886-36896. DOI URL
[6]	ZHANG J, ZANG X, WEN H, et al. High-voltage and free-standing poly(propylene carbonate)/Li_6.75La₃Zr_1.75Ta_0.25O₁₂ composite solid electrolyte for wide temperature range and flexible solid lithium ion battery. Journal of Materials Chemistry A, 2017,5(10):4940-4948.
[7]	XU D, SU J, JIN J, et al. In situ generated fireproof gel polymer electrolyte with Li_6.4Ga_0.2La₃Zr₂O₁₂ as initiator and ion-conductive filler. Advanced Energy Materials, 2019,9(25):1-12.
[8]	LI W W, ZHANG S P, WANG B R, et al. Nanoporous adsorption effect on alteration of the Li⁺ diffusion pathway by a highly ordered porous electrolyte additive for high-rate all-solid-state lithium metal batteries. ACS Appl. Mater. Inter., 2018,10(28):23874-23882. DOI URL
[9]	LIU Y, LEE J Y, HONG L. In situ preparation of poly(ethylene oxide)-SiO₂ composite polymer electrolytes. Journal of Power Sources, 2004,129(2):303-311.
[10]	ZHU P, YAN C, DIRICAN M, et al. Li_0.33La_0.557TiO₃ ceramic nanofiber-enhanced polyethylene oxide-based composite polymer electrolytes for all-solid-state lithium batteries. Journal of Materials Chemistry A, 2018,6(10):4279-4285. DOI URL
[11]	ZHAO C Z, ZHANG X Q, CHENG X B, et al. An anion- immobilized composite electrolyte for dendrite-free lithium metal anodes. Proc. Natl. Acad. Sci. USA, 2017,114(42):11069-11074. DOI URL PMID
[12]	LIU M, CHENG Z, GANAPATHY S, et al. Tandem interface and bulk Li-ion transport in a hybrid solid electrolyte with microsized active filler. ACS Energy Letters, 2019,4(9):2336-2342.
[13]	KUMAR B, SCANLON L G. Composite electrolytes for lithium rechargeable batteries. Journal of Electroceramics, 2000,5(2):127-139. DOI URL
[14]	LI W W, SUN C, JIN J, et al. Realization of the Li⁺ domain diffusion effect via constructing molecular brushes on the LLZTO surface and its application in all-solid-state lithium batteries. Journal of Materials Chemistry A, 2019,7(48):27304-27312.
[15]	HUANG Z Y, PANG W Y, LIANG P, et al. A dopamine modified Li_6.4La₃Zr_1.4Ta_0.6O₁₂-PEO solid-state electrolyte enhanced thermal and electrochemical properties. Journal of Materials Chemistry A, 2019,7:16425-16436.
[16]	YUAN C, LI J, HAN P, et al. Enhanced electrochemical performance of poly(ethylene oxide) based composite polymer electrolyte by incorporation of nano-sized metal-organic framework. Journal of Power Sources, 2013,240:653-658.
[17]	ZHOU L, ZHANG X H, CHEN Y L. Modulated synthesis of zirconium metal-organic framework UiO-66 with enhanced dichloromethane adsorption capacity. Materials Letters, 2017,197:167-170.
[18]	KINIK F P, UZUN A, KESKIN S. Ionic liquid/metal-organic framework composites: from synthesis to applications. ChemSusChem, 2017,10(14):2842-2863. DOI URL PMID
[19]	HUO H, WU B, ZHANG T, et al. Anion-immobilized polymer electrolyte achieved by cationic metal-organic framework filler for dendrite-free solid-state batteries. Energy Storage Materials, 2019,18:59-67.

固态锂电池用MOF/聚氧化乙烯复合聚合物电解质

MOF/Poly(Ethylene Oxide) Composite Polymer Electrolyte for Solid-state Lithium Battery

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 3

参考文献 19

相关文章 11

编辑推荐

Metrics

本文评价

[1]	郭宇翔, 黄立强, 王刚, 王宏志. 双锂盐凝胶复合电解质的制备及其在锂金属电池中的应用[J]. 无机材料学报, 2023, 38(7): 785-792.
[2]	陈鑫力, 李岩, 王伟胜, 石智文, 竺立强. 明胶/羧化壳聚糖栅控氧化物神经形态晶体管[J]. 无机材料学报, 2023, 38(4): 421-428.
[3]	谭淑雨, 刘晓宁, 毕志杰, 万勇, 郭向欣. 正极包覆与界面修饰: 双策略改善聚氧化乙烯固态电解质对高电压正极稳定性[J]. 无机材料学报, 2023, 38(12): 1466-1474.
[4]	蔡佳, 黄高旭, 金晓盼, 魏驰, 毛嘉毅, 李永生. 金属铋纳米颗粒原位修饰碳纳米管促进锂均匀沉积[J]. 无机材料学报, 2022, 37(12): 1337-1343.
[5]	李锐,王浩,付强,田子玉,王建旭,马小健,杨剑,钱逸泰. 构建亲锂铜基3D集流体实现金属锂的均匀沉积[J]. 无机材料学报, 2020, 35(8): 882-888.
[6]	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.
[7]	李栋, 雷超, 赖华, 刘小林, 姚文俐, 梁彤祥, 钟盛文. 全固态锂离子电池正极与石榴石型固体电解质界面的研究进展[J]. 无机材料学报, 2019, 34(7): 694-702.
[8]	罗世强, 郑春满, 孙巍巍, 谢威, 柯剑煌, 刘双科, 洪晓斌, 李宇杰, 许静. ZIF-67衍生Co-NC多孔碳材料的可控制备及其在锂-硫二次电池中的应用研究[J]. 无机材料学报, 2019, 34(5): 502-508.
[9]	李承斌, 岳红云, 王秋娴, 李静娴, 杨书廷. 锂离子电池陶瓷复合全固态电解质的制备和性能研究[J]. 无机材料学报, 2017, 32(8): 801-805.
[10]	黄乐之, 温兆银, 靳俊, 刘宇. 锂离子电池PEO-LATP/LAGP陶瓷复合电解质膜的制备与性能表征[J]. 无机材料学报, 2012, 27(3): 249-252.
[11]	陶善文,彭定坤,孟广耀. 无机盐-氧化物复合电解质导电机制[J]. 无机材料学报, 1999, 14(2): 203-210.