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- 2019
聚乙烯-乙烯醇磺酸锂/聚偏氟乙烯-六氟丙烯锂离子电池隔膜的制备及性能
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Abstract:
以聚乙烯-乙烯醇的磺化物（EVOH-SO3Li）和聚偏氟乙烯-六氟丙烯（PVDF-HFP）为原料，利用高压静电纺丝技术纺制成高孔隙率、纤维粗细均匀的EVOH-SO3Li/PVDF-HFP复合隔膜材料。利用FTIR、SEM、万能拉伸试验仪、TGA、BMP3电化学工作站和电池检测系统对EVOH-SO3Li/PVDF-HFP隔膜进行测试分析。测试结果表明：EVOH-SO3Li/PVDF-HFP隔膜形成致密的三维网络结构，纤维粗细均匀，孔径均一，EVOH-SO3Li/PVDF-HFP隔膜的孔隙率和吸液率分别为85%和437%；与纯EVOH-SO3Li隔膜相比，EVOH-SO3Li/PVDF-HFP复合隔膜的拉伸强度最大值从2.17 MPa提高至8.33 MPa，起始热分解温度升高至310℃，并表现出良好的电化学性能和电池性能。其中电化学稳定窗口由5.6 V增至5.8 V，界面阻抗由425.51 Ω降低至115.24 Ω，离子电导率由1.592×10-3 S/cm提高至3.102×10-3 S/cm；采用EVOH-SO3Li/PVDF-HFP隔膜组装的锂离子电池在0.5 C放电电流下循环100次后容量保持率为96.65%。 High-porosity and uniform-thickness composite separator was prepared by high-pressure electrospinning using polyethylene-vinyl alcohol sulfonate (EVOH-SO3Li) and poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) as raw materials. The performance of the EVOH-SO3Li/PVDF-HFP separator was characterized by FTIR, SEM, universal tensile tester, TGA, BMP3 electrochemical workstation and battery testing system. The test results show that the EVOH-SO3Li/PVDF-HFP separator forms a dense three-dimensional network structure with uniform fiber thickness and uniform pore size. The porosity and liquid absorption rate of EVOH-SO3Li/PVDF-HFP separator are 85% and 437%, respectively. Compared with pure EVOH-SO3Li separator, the maximum tensile strength of EVOH-SO3Li/PVDF-HFP composite separator is increased from 2.17 MPa to 8.33 MPa. The initial thermal decomposition temperature also raises to 310℃. The excellent performance of electrochemical and battery is exhibited. The electrochemical stability window is increased from 5.6 V to 5.8 V, the interfacial impedance is reduced from 425.51 Ω to 115.24 Ω, and the ionic conductivity is increased from 1.592×10-3 S/cm to 3.102×10-3 S/cm. Lithium-ion batteries assembled with EVOH-SO3Li/PVDF-HFP separators have a capacity retention rate of 96.65% after 100 cycles at 0.5 C discharge current. 山东省自然科学基金（ZR2011EMQ014）；国家自然科学基金（5160030627
| [1] | 邹才能, 赵群, 张国生, 等. 能源革命:从化石能源到新能源[J]. 天然气工业, 2016, 36(1):1-10.ZOU C N, ZHAO Q, ZHANG G S, et al. Energy revolution:From a fossil energy era to a new energy era[J]. Natural Gas Industry, 2016, 36(1):1-10(in Chinese). |
| [2] | 王振华, 彭代冲, 孙克宁. 锂离子电池隔膜材料研究进展[J]. 化工学报, 2018, 69(1):282-294.WANG Z H, PENG D C, SUN K N. Research progress of separator materials for lithium-ion batteries[J]. Journal of Chemical Industry and Engineering, 2018, 69(1):282-294(in Chinese). |
| [3] | HUANG X S. Separator technologies for lithium-ion batteries[J]. Journal of Solid State Electrochemistry, 2011, 15(4):649-662. |
| [4] | DI N V, LAVINA S, GIFFIN G A, et al. Polymer electrolytes:Past and future[J]. Electrochimica Acta, 2011, 57:4-13. |
| [5] | MIAO Y E, ZHU G N, HOU H Q, et al. Electrospun polyimide nanofiber-based nonwoven separators for lithium-ion batteries[J]. Journal of Power Sources, 2013, 226:82-86. |
| [6] | ZHANG H, ZHOU M Y, LIN C E, et al. Progress in polymeric separators for lithium ion batteries[J]. RSC Advance, 2015, 5(189):89848-89860. |
| [7] | MATABOLA K P, MOUTLOALI R M. The influence of electrospinning parameters on the morphology and diameter of poly(vinyledene fluoride) nanofibers-effect of sodium chloride[J]. Journal of Materials Science, 2013, 48(16):5475-5482. |
| [8] | 巩桂芬, 王磊, 李泽. 静电纺聚乙烯-乙烯醇磺酸锂/聚酰亚胺锂离子电池隔膜复合材料的电化学性能[J]. 复合材料学报, 2018, 35(10):2632-2639.GONG G F, WANG L, LI Z. Electrochemical properties of lithium ethylene-vinyl alcohol copolymer sulfate/polyimide Li-ion battery separator composite by electrospinning[J]. Acta Materiae Compositae Sinica, 2018, 35(10):2632-2639(in Chinese). |
| [9] | WANG C J, SHEN W Z, LU J, et al. Graphene oxide doped poly(vinylidene fluoride-co-hexafluoropropylene) gel electrode for lithium-ion battery[J]. Ionics, 2017, 23(8):2045-2053. |
| [10] | 闫金定. 锂离子电池发展现状及其前景分析[J]. 航空学报, 2014, 35(10):2767-2775.YAN J D. Current status and development analysis of lithium-ion batteries[J]. Acta Aeronautica et Astronautica Sinica, 2014, 35(10):2767-2775(in Chinese). |
| [11] | LI Z D, ZHANG Y C, XIANG H F, et al. Trimethyl phosphite as an electrolyte additive for high-voltage lithium-ion batteries using lithium-rich layered oxide cathode[J]. Journal of Power Sources, 2013, 240:471-475. |
| [12] | WANG Y R, YANG Y F, YANG Y B, et al. Enhanced electrochemical performance of unique morphological LiMnPO4/C cathode material prepared by solvothermal method[J]. Solid State Communications, 2010, 150(1-2):81-85. |
| [13] | 邹亚囡. 动力锂电池隔膜的改性研究进展[J]. 合成树脂及塑料, 2016, 33(6):87-90.ZOU Y N. Research progress of modification for power lithium-ion battery membrane[J]. China Synthetic Resin and Plastic, 2016, 33(6):87-90(in Chinese). |
| [14] | 夏清华. 锂离子电池新型隔膜技术及市场概况[J]. 广东化工, 2018, 45(8):172-173.XIA Q H. Technology and market of lithium-ion battery separator[J]. Guangdong Chemical Industry, 2018, 45(8):172-173(in Chinese). |
| [15] | YANG C L, LI Z H, LI W J, et al. Batwing-like polymer membrane consisting of PMMA-grafted electrospun PVDF-SiO2 nanocomposite fibers for lithium-ion batteries[J]. Journal of Membrane Science, 2015, 495(1):341-350. |
| [16] | CHEN J H, HU H J, LI S, et al. Evolution of mechanical properties of polypropylene separator in liquid electrolytes for lithium-ion batteries[J]. Journal of Applied Polymer Science, 2018, 135(7):6-11. |
| [17] | LIU S, ZHOU C, YU W. Phase separation and structure control in ultra-high molecular weight polyethylene micro-porous membrane[J]. Journal of Membrane Science, 2011, 379(1-2):268-278. |
| [18] | 刘太奇, 马福瑞, 赵云腾. 溶液聚偏氟乙烯静电纺纤维基超高分子量聚乙烯锂电池隔膜的制备[J]. 高分子材料科学与工程, 2015, 31(10):128-132.LIU T Q, MA F R, ZHAO Y T. Preparation of electrospun polyvinylidene fluoride fibers based UHMPWE lithium battery separator[J]. Polymer Materials Science & Engineering, 2015, 31(10):128-132(in Chinese). |
| [19] | 巩桂芬, 王磊, 徐阿文. 静电纺PMMA/EVOH-SO3Li复合锂离子电池隔膜的制备及性能[J]. 复合材料学报, 2018, 35(3):477-484.GONG G F, WANG L, XU A W. Preparation and properties of PMMA/EVOH-SO3Li Li-ion battery separator composite by electrospinning[J]. Acta Materiae Compositae Sinica, 2018, 35(3):477-484(in Chinese). |
| [20] | SPASOVA M, MANOLOVA N, MARKOVA N, et al. Tuning the properties of PVDF or PVDF-HFP fibrous materials decorated with ZnO nanoparticles by applying electrospinning alone or in conjunction with electrospraying[J]. Fibers and Polymers, 2017, 18(4):649-657. |
| [21] | 于宾, 焦晓宁. P(VDF-HFP)/Al2O3复合锂离子电池隔膜的电化学性能[J]. 电源技术, 2015, 39(4):702-705.YU B, JIAO X N. Electrochemical characterization of P(VDF-HFP)/Al2O3 composite separator for lithium-ion battery[J]. Chinese Journal of Power Sources, 2015, 39(4):702-705(in Chinese). |
