锂离子电池陶瓷复合全固态电解质的制备和性能研究

doi:10.15541/jim20160617

无机材料学报 ›› 2017, Vol. 32 ›› Issue (8): 801-805.DOI: 10.15541/jim20160617

锂离子电池陶瓷复合全固态电解质的制备和性能研究

李承斌^1,2, 岳红云³, 王秋娴³, 李静娴³, 杨书廷^1,3

(1. 河南师范大学物理与材料科学学院, 新乡453007; 2. 河南工学院电气工程系, 新乡453003; 3. 河南师范大学化学化工学院, 动力电源及关键材料国家地方联合工程实验室, 新乡453007)

收稿日期:2016-11-07 修回日期:2017-02-17 出版日期:2017-08-10 网络出版日期:2017-07-19
作者简介:李承斌(1984–), 男, 博士研究生. E-mail: milestone31@foxmail.com
基金资助:
国家自然科学基金(U1504211);河南省科技攻关项目(142102210449)

Preparation and Property of a Novel Heat-resistant Ceramic Composite Solid-state Electrolyte for Lithium Batteries

LI Cheng-Bin^1,2, YUE Hong-Yun³, WANG Qiu-Xian³, LI Jing-Xian³, YANG Shu-Ting^1,3

(1. College of Physics and Materials Science, Henan Normal University, Xinxiang 453007, China; 2. Department of Electrical Engineering, Henan Institute of Technology, Xinxiang 453003, China; 3. National and Local Joint Engineering Laboratory of Motive Power and Key Materials, School of Chemistry and Chemical Engineering, Henan Normal University Xinxiang 453007, China)

Received:2016-11-07 Revised:2017-02-17 Published:2017-08-10 Online:2017-07-19
About author:LI Cheng-Bin. E-mail: milestone31@foxmail.com
Supported by:
National Natural Science Foundation of China (U1504211);Science and Technology Project of Henan Province (142102210449)

摘要/Abstract

摘要：

以负载Al₂O₃的无纺布为支撑膜, 浸涂PEO-LAGP-SN-LiTFSI的乙腈共混液干燥后制得新型复合固态电解质膜(CLASP)。该膜的热稳定性好, 即使在170℃的高温下依然不发生形变。当浸涂共混液中PEO: LAGP: SN: LiTFSI为3: 1: 1: 1, 固含量为10wt%时, 室温电导率可以达到3.66×10^-5 S/cm, 100℃时电导率可达2.52×10^-4 S/cm. CLASP膜的电化学窗口宽, 以该膜代替液态电解质装配的全固态LiFePO₄/CLASP/Li电池, 在55℃循环时表现出良好的循环稳定性, 高的库伦效率, 有望成为电化学性能优越的全固态电解质。

关键词: 全固态, 复合电解质, 磷酸锗铝锂, 耐热

Abstract:

Poly(ethylene oxide) (PEO) as a kind of promising candidates of polymer electrolyte is widely applied in all solid lithium ion batteries. In this study, a novel ceramic composite solid electrolyte (CLASP) was prepared by dip-coating PEO-LAGP-SN-LiTFSI (PEO-SPE) into Al₂O₃ nonwoven membrane. And all solid batteries were assembled with CLASP. CLASP showed excellent thermostability even at 170℃ for 2 h. When the ratio of PEO: LAGP: SN: LiTFSI was 3: 1: 1: 1, the conductivities of CLASP reached 3.66×10^-5 S/cm at 25℃ and 2.52×10^-4 S/cm at 100℃, respectively. The electrochemical window of CLASP was 5.5 V, which had great potential to apply in battery with high voltage cathode material. The cycling performance of all solid batteries with CLASP was greatly improved at 55℃ as well. This new ceramic composite, solid polymer electrolyte, with all these outstanding performance is a promising candidate of all solid electrolytes.

Key words: all solid state, composite electrolyte, LAGP, heat-resistance

中图分类号:

Q152

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.

LI Cheng-Bin, YUE Hong-Yun, WANG Qiu-Xian, LI Jing-Xian, YANG Shu-Ting. Preparation and Property of a Novel Heat-resistant Ceramic Composite Solid-state Electrolyte for Lithium Batteries[J]. Journal of Inorganic Materials, 2017, 32(8): 801-805.

图/表 4

图1 (a) PEO, SN, LiTFSI, LAGP, PEO-SPE, FS-25无纺布和CLASP的红外光谱图; (b) LAGP的XRD图谱和粒径分布图; (c) FS-25无纺布和CLASP的XRD图谱

Fig. 1 (a) ATR-FTIR spectra of PEO, SN, LiTFSI, LAGP, PEO-SPE, bare FS-25, and CLASP; (b) XRD pattern of LAGP and the LAGP particle diameter distribution (inset); (c) XRD patterns of bare FS-25 and CLASP

图2 无纺布FS-25和CLASP的表面(a, b/d,e)和截面(c/f)的SEM照片

Fig. 2 Surface and cross-section SEM images of bare FS-25 (a, b and c) and CLASP (d, e and f)

图3 PEO, SN, PEO-SPE, FS-25无纺布和CLASP的DSC曲线

Fig. 3 DSC curves for PEO, SN, PEO-SPE, bare FS-25, and CLASP Inset is the shrinkage pictures of PP, bare FS-25 and CLASP after treatment at 170℃for 2 h

图4 (a)不同温度下LAGP、PEO固态电解质和CLASP的离子电导率, (b)CLASP的线性伏安扫描图, (c)55℃, 0.1C下用CLASP组装的全固态电池前三个循环的电压-比容量曲线和(d) 55℃, 0.1 C下用CLASP组装的全固态电池循环图

Fig. 4 (a) Temperature dependence of ionic conductivity for LAGP, PEO-SPE and CLASP; (b) LSV curve for CLASP; the first three charge/discharge voltage profiles (c) and cycling performance (d) of the LiFePO4/Li cell using CLASP at 0.1C, 55℃

参考文献 18

[1]	XUE Z G, HE D, XIE X L.Poly(ethylene oxide)-based electrolytes for lithium ion batteries.Journal of Materials Chemistry A, 2015, 3(7): 19218-19253.
[2]	GOODENOUGH J B, KIM Y.Challenges for rechargeable Li batteries.Chemistry Materials, 2010, 22(3): 587-603.
[3]	ZHENG Y L, CEHN R J, WU F, et al.Progress of research on the conductive mechanism of the glassy electrolytes in lithium ion batteries. Journal of Inorganic Materials, 2013, 28(11): 1172-1180.
[4]	ZHOU W D, WANG S F, LI Y T, et al.Plating a dendrite-free lithium anode with a polymer/ceramic/polymer sandwich electrolyte.Journal of the American Chemical Society, 2016, 138(7): 9385-9388.
[5]	CHEN B, HUANG Z, CHEN X T, et al.A new composite solid electrolyte PEO/Li10GeP2S12/SN for all-solid-state lithium battery.Electrochim. Acta, 2016, 210(6): 905-914.
[6]	HU P, CHAI J C, DUAN Y L, et al.Progress in nitrile-based polymer electrolytes for high performance lithium batteries. Journal of Materials Chemistry A, 2016, 4(5): 10070-10083.
[7]	LU Y, KORF K, KAMBE Y, et al.Ionic liquid nanoparticle hybrid electrolytes: applications in lithium metal batteries. Angewandte Chemie, 2014, 126(2): 498-502.
[8]	CHEN X, USREY M, PENA H A, et al.Thermal and electrochemical stability of organosilicon electrolytes for lithium-ion batteries.Journal of Power Sources, 2013, 241(1): 311-319.
[9]	ZHANG H, LIU C Y, ZHENG Li P, et al.Lithium bis (fluorosulfonyl)imide/poly(ethylene oxide) polymer electrolyte.Electrochimca Acta, 2014, 133(4): 529-538.
[10]	ZHAO Y R, HUANG Z, CHEN S J, et al.A promising PEO/LAGP hybrid electrolyte prepared by a simple method for all-solid-state lithium batteries. Solid State Ionics, 2016, 295(8): 65-71.
[11]	PITAWALA H M J C, DISSANAYAKE M A K L, SENEVIRATNE V A. Combined effect of Al2O3 nano-fillers and EC plasticizer on ionic conductivity enhancement in the solid polymer electrolyte (PEO)9LiTf.Solid State Ionics, 2007, 178(4): 885-888.
[12]	TARASCON J M, ARMAND M.Issues and challenges facing rechargeable lithium batteries.Nature, 2001, 414(11): 359-367.
[13]	CHOI J H, LEE C H, YU J H, et al.Enhancement of ionic conductivity of composite membranes for all-solid-state lithium rechargeable batteries incorporating tetragonal Li7La3Zr2O12 into a polyethylene oxide matrix.Journal of Power Sources, 2015, 274(10): 458-463.
[14]	SHARMA M V N V D, SARMA A V, RAO R B. Electrical conductivity, relaxation, and scaling analysis studies of lithium alumino phosphate glasses and glass ceramics.Journal of Materials Science, 2009, 44(2): 5557-5562.
[15]	HUANG L Z, WEN Z Y, JIN J, et al.Preparation and characterization of PEO-LATP/LAGP ceramic composite electrolyte membrane for lithium batteries.Journal of Inorganic Materials, 2012, 27(3): 249-252.
[16]	JIN L Y, JIANG Y X, LIAO H G, et al.FTIR spectroscopic studies of PEO-based polymer electrolyte with ionic liquid.Chemical Journal of Chinese University, 2009, 30(4): 767-771.
[17]	YAN B G, ZHU Y Q, PAN F, et al.Li1.5Al0.5Ge1.5(PO4)3 Li-ion conductor prepared by melt-quench and low temperature pressing.Solid State Ionics, 2015, 278(6): 65-68.
[18]	MOHD R J, OON H S, SURIANI I, et al.Effects of Al2O3 nanofiller and EC plasticizer on the ionic conductivity enhancement of solid PEO-LiCF3SO3 solid polymer electrolyte.Solid State Ionics, 2011, 196(7): 41-47.

锂离子电池陶瓷复合全固态电解质的制备和性能研究

Preparation and Property of a Novel Heat-resistant Ceramic Composite Solid-state Electrolyte for Lithium Batteries

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 4

参考文献 18

相关文章 15

编辑推荐

Metrics

本文评价

[1]	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.
[2]	夏求应, 孙硕, 昝峰, 徐璟, 夏晖. 非晶LiSiON薄膜电解质的全固态薄膜锂电池性能[J]. 无机材料学报, 2022, 37(2): 230-236.
[3]	王天悦, 王梦颖, 黄庆姣, 杨佳明, 王顺花, 刁训刚. 溶胶-凝胶旋涂法制备电致变色智能窗用钛酸锂薄膜[J]. 无机材料学报, 2021, 36(5): 471-478.
[4]	贾汉祥, 邵泽伟, 黄爱彬, 金平实, 曹逊. 光学设计用于全固态电致变色器件的高溅射效率三明治结构电解质[J]. 无机材料学报, 2021, 36(5): 479-484.
[5]	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.
[6]	贾汉祥, 曹逊, 金平实. 无机全固态电致变色材料与器件研究进展[J]. 无机材料学报, 2020, 35(5): 511-524.
[7]	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.
[8]	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.
[9]	董宇辉, 曾书玉, 韩博宁, 薛洁, 宋继中, 曾海波. BN/CsPbX₃复合纳米晶的制备及其白光LED应用[J]. 无机材料学报, 2019, 34(1): 72-78.
[10]	潘国祥, 陈健, 倪哲明, 曹枫, 胡双双, 林凯, 李金花, 竺增林. 包覆型氧化铁黄颜料微结构与耐热性能研究[J]. 无机材料学报, 2016, 31(1): 75-80.
[11]	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.
[12]	徐军,苏良碧,徐晓东,赵志伟,赵广军. 激光晶体的现状及发展趋势[J]. 无机材料学报, 2006, 21(5): 1025-1030.
[13]	方玉堂,丁静,范娟,杨建平,杨晓西. 新型铝改性硅胶吸附材料的制备与性能[J]. 无机材料学报, 2005, 20(4): 933-939.
[14]	祝琳华,廖学品,郎小川,杨劲. 磷酸盐陶瓷Ca_1-xBa_xZr₄(PO₄)₆的制备及其零膨胀组成的耐热冲击性研究[J]. 无机材料学报, 2001, 16(3): 452-458.
[15]	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.