Preparation and properties of polyphosphazene modified composite separator for lithium-ion battery
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摘要: 锂离子电池要求隔膜具有良好的亲液性和耐热性。本文设计原位限域聚合法，利用聚(环三磷腈-4, 4-磺酰基二苯酚)微球(PZSMS)修饰聚偏氟乙烯(PVDF)纤维基膜，通过单体与引发剂分别引入的策略调控PZSMS的尺寸和分布，促进PVDF纤维表面连续包覆层的形成，获得新型复合膜。对隔膜的理化性能(孔道结构、力学性能、电解液性能和耐热性)和电池性能(循环性能、倍率性能)进行系统研究。结果表明：在优化条件下，复合膜的吸液率和离子电导率分别达到433%和1.47 mS/cm，拉伸强度大于25 MPa，且在150℃、0.5 h内热收缩率低于2%，优于PVDF基膜及市售聚乙烯隔膜(PE)隔膜。在钴酸锂/石墨电池中，优化的复合膜显示出较好的电池充放电性能，如8.0 C时的放电容量为0.5 C时的76%，200次循环后放电容量保持率为97%。因此，原位限域聚合法制备的PZSMS修饰PVDF纤维膜在锂离子电池中显示出较好的应用前景。Abstract: Separators with superior electrolyte property and thermal stability are in urgent need for lithium-ion batteries (LIBs). This work designed a space-confined polymerization method to fabricate an advanced composite separator, in which poly(cyclotriphosphazene-co-4, 4-sulfonyldiphenol) microspheres (PZSMS) grow directly in poly(vinylidene fluoride) (PVDF) membrane as the substrate. To regulate the size and distribution of PZSMS, triethylamine vapor as acid-binding agent is introduced into PVDF membrane separately from the polymeric monomers. The physical-chemical properties and battery performances of PPCS were systematically characterized, such as the structure, tensile strength, electrolyte property and thermal resistance as well as the charge-discharge performance. The results show that under the optimized conditions, the liquid absorbency and ionic conductivity of the composite membrane reach 433% and 1.47 mS/cm, respectively, the tensile strength is greater than 25 MPa, and the thermal shrinkage rate is lower than 2% at 150℃ and 0.5 h, which is better than that of PVDF based membrane and commercial polyethylene (PE) membrane. The LiCoO2/graphite cells with optimized separators exhibit satisfactory discharge capacity retention of 76% at 8.0 C compared with that at 0.5 C and preferable cycling stability with a capacity retention of 97% after 200 cycles. Therefore, PZSMS modified PVDF fibrous membrane prepared by space-confined polymerization method shows a good application prospect in lithium-ion batteries.
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图 1 六氯环三磷腈(HCCP)、4, 4'-二羟基二苯砜(BPS)单体和含磷聚合物(PZS)的分子结构
Figure 1. Molecular structures of hexachlorocyclotriphosphazene (HCCP), 4, 4'-dihydroxy diphenyl sulfone (BPS) and phosphorous polymer (PZS)
TEA—Triethylamine
图 2 ((a)~(f)) 不同膜样品的SEM图像；((g)~(l)) PP-2.0膜局部的EDS分布图
Figure 2. ((a)-(f)) SEM images of different separators; ((g)-(l)) EDS mapping of PP-2.0 separator
图 3 膜样品的FTIR图谱(a)、PZSMS负载量(b)、平均孔径/孔隙率(c)及拉伸强度(d)
Figure 3. FTIR spectra (a), PZSMS loadings (b), average pore-size/porosity (c) and tensile strength (d) of separator samples
PE—Polyethylene
图 4 PP-2.0膜及其超声处理不同时间后的SEM图像
Figure 4. SEM images of PP-2.0 separator before and after ultrasonic treatment for different time
图 5 不同膜材料的电解液亲和性((a)~(c))和耐热性(150℃, 0.5 h) ((d)~(f))
Figure 5. Electrolyte wettability ((a)-(c)) and thermal resistance ((d)-(f)) of different separators (150℃ for 0.5 h)
图 6 不同隔膜装配Li/不锈钢片(SS)模拟电池的LSV图(a)和装配SS/SS模拟电池的Nyquist图(b)
Figure 6. LSV spectra of Li/stainless steel (SS) cells (a) and Nyquist plots of SS/SS cells (b) with different separators
Rb—Bulk resistance of the separator
图 7 PE膜(a)和PP-2.0膜(b)装配电池的首次充放电曲线
Figure 7. First charge-discharge curves of the cells with PE separator (a) and PP-2.0 separator (b)
图 8 不同隔膜装配钴酸锂/石墨电池的倍率容量保持性(a)和循环稳定性(b)
Figure 8. C-rate capacity retention (a) and cycling stability (b) of LiCoO2/graphite cells with different separators
图 9 经过200次循环测试后PP-2.0膜的表面SEM图像
Figure 9. SEM image of PP-2.0 separator after 200 charge-discharge cycles
表 1 聚偏氟乙烯(PVDF)-聚(环三磷腈-4,4-磺酰基二苯酚)微球(PZSMS)复合隔膜的命名
Table 1. Sample naming of poly(vinylidene fluoride) (PVDF)-poly(cyclotriphosphazene-co-4,4-sulfonyldiphenol) microspheres (PZSMS) composite separator
Sample Reaction time/h PVDF — PP-0.5 0.5 PP-1.0 1.0 PP-2.0 2.0 PP-4.0 4.0 CP-2.0 2.0 Notes: PP—PVDF-PZSMS composite separator; CP—Conven-tional composite separator. 
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表 2 静置不同时间后PE、PP-2.0及CP-2.0膜的界面电阻(Rint)
Table 2. Interfacial resistance (Rint) of PE, PP-2.0, CP-2.0 separators as a function of stabilization time
Sample Rint 1 d 3 d 5 d 7 d PE 303 423 525 571 PP-2.0 249 291 335 355 CP-2.0 270 361 436 464
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