EVOH-SO<sub>3</sub>Li/P(VDF-HFP)/HAP锂离子电池隔膜的制备及电化学性能

doi:10.11868/j.issn.1001-4381.2018.001320

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摘要

以聚偏氟乙烯-六氟丙烯（P（VDF-HFP））、纳米羟基磷灰石（HAP）和聚乙烯-乙烯醇共聚物的磺化物（EVOH-SO₃Li）为原料进行高压共混静电纺丝，制备出EVOH-SO₃Li/P（VDF-HFP）/HAP锂离子电池隔膜。利用FTIR，SEM，电化学工作站和电池检测系统对隔膜进行测试分析。结果表明：EVOH-SO₃Li隔膜为粗细均匀的三维网络结构，加入P（VDF-HFP）和HAP后，EVOH-SO₃Li/P（VDF-HFP）/HAP复合隔膜呈现出树枝形状的三维网状结构，提高了隔膜的孔隙率和吸液率，与纯EVOH-SO₃Li隔膜相比，分别提高了37.5%和91.6%。同时表现出良好的电化学性能，组装的锂离子电池的电化学稳定窗口为5.65 V，界面阻抗降至184.24 Ω，离子电导率则提高至2.686×10^-3 S·cm^-1；在0.5 C放电电流下循环100次后容量保持率为96.69%，与EVOH-SO₃Li隔膜相比各项性能均有所提高。

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关键词 ：锂离子电池隔膜, 聚偏氟乙烯-六氟丙烯, EVOH-SO₃Li, 纳米羟基磷灰石, 静电纺丝

Abstract：

EVOH-SO₃Li/P(VDF-HFP)/HAP lithium ion battery separator was prepared by high-pressure blending electrospinning using polyethylene-vinyl alcohol sulfonate (EVOH-SO₃Li), poly(vinylidene fluoride-hexafluoropropylene) (P(VDF-HFP)) and nano hydroxyapatite (HAP) as raw materials. The performance of the separator was characterized by FTIR, SEM, electrochemical workstation and battery detection system. The results show that the EVOH-SO₃Li/P(VDF-HFP) composite separator forms an uniform and dense three-dimensional network structure, and the EVOH-SO₃Li/P(VDF-HFP)/HAP composite separator presents a three-dimensional network of dendritic shapes after adding P(VDF-HFP) and HAP, which improves the porosity and liquid absorption rate of the separator. Compared with the pure EVOH-SO₃Li separator, the porosity and liquid absorption rate of the EVOH-SO₃Li/P(VDF-HFP)/HAP composite separator are increased by 37.5% and 91.6%, respectively. Meanwhile, the excellent electrochemical performance is also exhibited. The electrochemical stability window of the assembled lithium-ion battery is 5.65 V, and the interfacial impedance is decreased to 184.24 Ω, and the ionic conductivity is increased to 2.686×10^-3 S·cm^-1; Lithium-ion batteries assembled with EVOH-SO₃Li/P(VDF-HFP)/HAP composite separator have a capacity retention rate of 96.69% after 100 cycles at 0.5 C discharge current, the properties of EVOH-SO₃Li/P(VDF-HFP)/HAP composite separator are improved compared with EVOH-SO₃Li.

Key words： lithium-ion battery separator poly(vinylidene fluoride-hexafluoropropylene) EVOH-SO₃Li nano hydroxyapatite electrospinning

收稿日期: 2018-11-12 出版日期: 2020-05-28

中图分类号:

TQ340.64

基金资助:山东省自然科学基金(ZR2011EMQ014);国家自然科学基金(5160030627)

通讯作者: 巩桂芬 E-mail: ggf-hust@163.com

作者简介: 巩桂芬(1966-), 女, 教授, 博士, 主要从事纳米纤维素制备及改性、超疏水材料和锂离子电池隔膜的研究, 联系地址:黑龙江省哈尔滨市南岗区征仪路249号哈尔滨理工大学材料科学与工程学院412室(150040), E-mail:ggf-hust@163.com

引用本文:

巩桂芬, 徐阿文, 邹明贵, 邢韵, 辛浩. EVOH-SO₃Li/P(VDF-HFP)/HAP锂离子电池隔膜的制备及电化学性能[J]. 材料工程, 2020, 48(5): 75-82.
Gui-fen GONG, A-wen XU, Ming-gui ZOU, Yun XING, Hao XIN. Preparation and electrochemical properties of EVOH-SO₃Li/poly(vinylidene fluoride-hexafluoropropylene)/hydroxyapatite lithium-ion battery separator. Journal of Materials Engineering, 2020, 48(5): 75-82.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2018.001320 或 http://jme.biam.ac.cn/CN/Y2020/V48/I5/75

Fig.1 EVOH-SO₃Li，EVOH-SO₃Li/PVDF-HFP和EVOH-SO₃Li/P(VDF-HFP)/HAP隔膜的红外图谱

Fig.2 Celgard PP(a)，EVOH-SO₃Li(b), EVOH-SO₃Li/P(VDF-HFP)(c)和EVOH-SO₃Li/P(VDF-HFP)/HAP(d)隔膜的微观形貌

Fig.3 EVOH-SO₃Li/P(VDF-HFP)/HAP复合隔膜中两个不同区域下的高倍SEM图
(a)图 2(d)中区域A的SEM图；(b)图 2(d)中区域B的SEM图

Table 1 Celgard PP，EVOH-SO₃Li，EVOH-SO₃Li/P(VDF-HFP)和EVOH-SO₃Li/P(VDF-HFP)/HAP隔膜孔隙率和吸液率

Fig.4 Celgard PP，EVOH-SO₃Li，EVOH-SO₃Li/P(VDF-HFP)和EVOH-SO₃Li/P(VDF-HFP)/HAP隔膜的电化学稳定窗口

Fig.5 Celgard PP, EVOH-SO₃Li, EVOH-SO₃Li/P(VDF-HFP)和EVOH-SO₃Li/P(VDF-HFP)/HAP隔膜的界面阻抗

Fig.6 Celgard PP，EVOH-SO₃Li，EVOH-SO₃Li/P(VDF-HFP)和EVOH-SO₃Li/P(VDF-HFP)/HAP复合隔膜的交流阻抗图谱

Table 2 Celgard PP，EVOH-SO₃Li，EVOH-SO₃Li/P(VDF-HFP)和EVOH-SO₃Li/P(VDF-HFP)/HAP隔膜的物理参数

Fig.7 Celgard PP，EVOH-SO₃Li，EVOH-SO₃Li/P(VDF-HFP)和EVOH-SO₃Li/P(VDF-HFP)/HAP复合隔膜组装锂电池的循环性能

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