静电纺<strong>TiO<sub>2</sub></strong>改性联苯型聚酰亚胺锂离子电池隔膜

doi:10.11901/1005.3093.2019.429

材料研究学报

2020, Vol. 34

Issue (3): 169-175 DOI: 10.11901/1005.3093.2019.429

研究论文

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静电纺TiO₂改性联苯型聚酰亚胺锂离子电池隔膜

巩桂芬¹(

),李泽¹,王磊²,崔巍巍¹

1. 哈尔滨理工大学材料科学与工程学院哈尔滨 150040
2. 哈尔滨工程大学材料科学与化学工程学院哈尔滨 150001

Electrospinning TiO₂ Modified Biphenyl Polyimide Lithium Ion Battery Separator

GONG Guifen¹(

),LI Ze¹,WANG Lei²,CUI Weiwei¹

1. School of Materials Science and Engineering，Harbin University of Science and Technology，Harbin 150040，China
2. College of Materials Science and Chemical Engineering，Harbin Engineering University，Harbin 150001，China

引用本文:

巩桂芬,李泽,王磊,崔巍巍. 静电纺TiO₂改性联苯型聚酰亚胺锂离子电池隔膜[J]. 材料研究学报, 2020, 34(3): 169-175.
Guifen GONG, Ze LI, Lei WANG, Weiwei CUI. Electrospinning TiO₂ Modified Biphenyl Polyimide Lithium Ion Battery Separator[J]. Chinese Journal of Materials Research, 2020, 34(3): 169-175.

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摘要:

先采用高压静电纺丝技术制备二氧化钛/聚酰胺酸(TiO₂/PAA)复合纤维膜，然后对其进行热亚胺化处理制备出二氧化钛/聚酰亚胺(TiO₂/PI)复合纤维隔膜。使用扫描电子显微镜(SEM)、傅里叶红外光谱分析仪(FTIR)、热失重分析仪和电化学工作站测试了TiO₂/PI复合纤维隔膜的基本性能和电化学性能，结果表明：隔膜具有明显的三维网状结构，与未改性的纯PI隔膜相比，改性后TiO₂/PI复合纤维隔膜的拉伸强度、孔隙率和吸液率分别提高到16.74 MPa、77.5%和550%；其热收缩性能较好，整体电化学性能优异。制备的LiFePO₄(磷酸铁锂正极)/TiO₂/PI/C(石墨负极)电池具有优异的循环稳定性和高放电容量，在1 C条件下进行100个循环后，其库伦效率在25℃和120℃高达96.7%和90.7%。

关键词 ：有机高分子材料, TiO₂, 联苯型聚酰亚胺, 锂离子电池隔膜, 高压静电纺丝, 电化学性能

Abstract：

TiO₂/PAA composite fiber membranes were prepared by high-voltage electrospinning, and then were thermally imidized to obtain TiO₂/PI composite fiber membranes. The physical properties, mechanical properties and electrochemical properties of TiO₂/PI composite fiber separators were assessed by means of scanning electron microscope, Fourier infrared spectrometer, thermogravimetric analyzer and electrochemical workstation. The results show that the membrane have clear three-dimensional network structure, and the tensile strength, the porosity and the liquid absorption rate of the modified TiO₂/PI composite membrane increase to 16.74 MPa, 77.5% and 550%, respectively comparing with the plain PI membrane; the membrane have good thermal shrinkage performance; excellent overall electrochemical performance; the prepared Li-battery of LiFePO₄ (lithium iron phosphate positive electrode)/TiO₂/PI/C (graphite negative electrode) presents excellent cycle stability and high discharge capacity, after 100 cycles at 1 C、at 25°C and 120°C, the cell coulombic efficiency is as high as 96.7% and 90.7%, respectively.

Key words： organic polymer materials TiO₂ biphenyl polyimides lithium battery separator electro-spinning electrochemical property

收稿日期: 2019-09-03

ZTFLH:

TQ322.4+2

基金资助:国家自然科学基金(51603075)

作者简介: 巩桂芬，女，1966年生，博士

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https://www.cjmr.org/CN/10.11901/1005.3093.2019.429 或 https://www.cjmr.org/CN/Y2020/V34/I3/169

图1 隔膜的红外光谱图

图2 不同TiO2含量的TiO2/PI复合纤维膜的SEM照片

表1 不同TiO2含量的TiO2/PI复合隔膜的孔隙率

图3 不同TiO2含量的TiO2/PI复合隔膜的吸液率

图4 不同TiO2含量的TiO2/PI复合隔膜的TG曲线

表2 PP、PI和TiO2/PI隔膜分别在100、150、200和250℃热处理后的尺寸稳定性

图5 不同TiO2含量的TiO2/PI复合隔膜的TG曲线

图6 隔膜的电化学稳定窗口

图7 PP、PI和TiO2/PI隔膜的Nyquist图 (a) “Li/隔膜/Li”体系, (b) “SS/隔膜/SS”体系

图8 使用PP、PI和TiO2/PI复合隔膜装配的电池在1 C和不同温度的循环寿命图

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