Preparation and performance of flame-retardant safety PES@SiO2 lithium-ion battery separator
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摘要:
锂离子电池具有高比能量密度、良好的循环性能及环境友好等特性，使其在电动汽车、电子产品、储能等领域广泛应用。但近年来锂离子电池在使用过程中频繁发生安全事故，使得人们对这种清洁能源的安全性提出了质疑。聚醚砜(PES)隔膜具有优异的耐高温尺寸稳定性，同时在阻燃性能方面表现也很突出，本文通过静电纺丝技术，使得制备的PES电池隔膜具有良好的孔隙率，对电解液有更好的浸润性。利用原位生长技术在PES纳米纤维的表面包覆一层SiO2，使隔膜在力学性能以及耐热稳定上得以提高，同时无机粒子SiO2在高温灼烧下缩聚交联成Si—O—Si网状结构层阻断燃烧的特性又赋予隔膜阻燃的性能，通过扫描电子显微镜(SEM)对复合隔膜的微观形貌进行表征，以及傅里叶红外光谱(FTIR)对复合隔膜的微观结构进行表征等，通过对纤维隔膜进行点火器灼烧，表征了复合隔膜的阻燃特性，其中PES/SiO2-1.5隔膜的阻燃性最好，同时在电化学性能方面表现也十分优异。
Abstract:Lithium-ion batteries, renowned for their high energy density, robust cycle life, and environmentally friendly profile, have found extensive applications in sectors such as electric vehicles, consumer electronics, and energy storage systems. Despite their widespread adoption, the increasing frequency of safety incidents during lithium-ion battery usage in recent years has cast doubt on the safety and reliability of this clean energy technology. Polyethersulfone (PES) membranes demonstrate superior dimensional stability at elevated temperatures, along with exceptional flame-retardant properties. In this work, PES-based separators were fabricated via electrospinning, yielding membranes with optimized porosity and enhanced electrolyte wettability. Through the application of in-situ growth techniques, a SiO2 layer was uniformly coated onto the PES nanofibers, enhancing both the mechanical properties and thermal stability of the separators. The inorganic SiO2 nanoparticles undergo polycondensation and cross-linking under high temperatures, forming a Si—O—Si network that effectively inhibits combustion, thus imparting flame-retardant capabilities to the membranes. The microstructure of the composite membranes was systematically characterized using scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR).Flame retardancy was assessed via ignition testing, revealing that the PES/SiO2-1.5 membrane demonstrated superior flame resistance, along with remarkable electrochemical performance.
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Keywords:
- lithium-ion batteries /
- Diaphragm /
- Flame retardant /
- Electrospinning /
- in situ growth
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图 2 TEOS合成SiO2微球的水解缩合反应过程
Figure 2. The hydrolysis and condensation reaction process of TEOS synthesis of SiO2 microspheres
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图 3 (a)-(d) PES、PES/SiO2-0.5、PES/SiO2-1.0、PES/SiO2-1.5在
5000 ×下的SEM图; (e)-(h) PES、PES/SiO2-0.5、PES/SiO2-1.0、PES/SiO2-1.5在20000 ×下的SEM图; (i)-(l) PES、PES/SiO2-0.5、PES/SiO2-1.0、PES/SiO2-1.5在100000 ×下的SEM图Figure 3. (a)-(d) SEM images of PES, PES/SiO2-0.5, PES/SiO2-1.0, and PES/SiO2-1.5 at
5000 ×; (e)-(h) SEM images of PES, PES/SiO2-0.5, PES/SiO2-1.0, and PES/SiO2-1.5 at20000 ×;(i)-(l) SEM images of PES, PES/SiO2-0.5, PES/SiO2-1.0, and PES/SiO2-1.5 at 100000×
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图 4 PES、PES/SiO2-0.5、PES/SiO2-1.0、PES/SiO2-1.5的FTIR图谱
Figure 4. FTIR Spectra of PES、PES/SiO2-0.5、PES/SiO2-1.0、PES/SiO2-1.5
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图 5 PES、PES/SiO2-0.5、PES/SiO2-1.0、PES/SiO2-1.5的XRD图谱
Figure 5. XRD patterns of PES, PES/SiO2-0.5, PES/SiO2-1.0, PES/SiO2-1.5
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图 6 PES、PES/SiO2-0.5、PES/SiO2-1.0、PES/SiO2-1.5纤维复合隔膜的力学性能柱状图
Figure 6. Histogram of mechanical properties of PES, PES/SiO2-0.5, PES/SiO2-1.0 and PES/SiO2-1.5 fiber composite separators
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图 7 Celgard、PES、PES/SiO2-0.5、PES/SiO2-1.0、PES/SiO2-1.5纤维复合隔膜(a)吸液率随时间变化的曲线(b)饱和吸液率和孔隙率柱状图(c)接触角图片
Figure 7. Celgard, PES, PES/SiO2-0.5, PES/SiO2-1.0, PES/SiO2-1.5 fiber composite septums (a) Curves of liquid absorption over time (b) Saturated absorption and porosity histogram (c) Contact angle image
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图 8 Celgard、PES、PES/SiO2-0.5、PES/SiO2-1.0、PES/SiO2-1.5隔膜的热收缩图片
Figure 8. Heat shrink image of Celgard, PES/SiO2-0.5, PES/SiO2-1.0, PES/SiO2-1.5 diaphragm
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图 9 Celgard、PES、PES/SiO2-0.5、PES/SiO2-1.0、PES/SiO2-1.5隔膜的电化学窗口曲 线
Figure 9. Electrochemical window curves of Celagard , PES/SiO2-0.5 , PES/SiO2-1.0 ,PES/SiO2-1.5 separator
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图 10 Celgard、PES、PES/SiO2-0.5、PES/SiO2-1.0、PES/SiO2-1.5隔膜的界面阻抗
Figure 10. Interfacial impedance of Celgard、PES、PES/SiO2-0.5、PES/SiO2-1.0、PES/SiO2-1.5 separator
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图 11 Celgard、PES、PES/SiO2-0.5、PES/SiO2-1.0、PES/SiO2-1.5隔膜的交流阻抗图谱
Figure 11. AC impedance maps of Celgard、PES、PES/SiO2-0.5、PES/SiO2-1.0、PES/SiO2-1.5 separator
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图 12 PES、PES/SiO2-0.5、PES/SiO2-1.0、PES/SiO2-1.5隔膜在点火器灼烧下不同时间的形貌图片
Figure 12. Pictures of the morphology of PES, PES/SiO2-0.5, PES/SiO2-1.0, and PES/SiO2-1.5 diaphragms at different times under the ignition burn
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图 14 Celgard、PES、PES/SiO2-1.5隔膜的循环性能曲线
Figure 14. Cyclic performance curves of Celgard、PES、PES/SiO2-1.5 separator
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图 15 Celgard、PES、PES/SiO2-1.5隔膜的倍率性能曲线
Figure 15. Magnanimity performance curves of Celgard、PES、PES/SiO2-1.5 separator
表 1 制备 SiO2微球的前驱体溶液样品及用量
Table 1 Precursor solution samples and dosage of SiO2 microspheres
Sample CTEOS
/(mol·L-1)MTEOS
/gVabsolute ethanol
/mLVammonia
/mLPES/SiO2-0.5 0.5 5.2 50 3 PES/SiO2-1.0 1.0 10.4 50 3 PES/SiO2-1.5 1.5 15.6 50 3 Notes: PES is Polyethersulfone; CTEOS is the concentration of TEOS, in mol/L; MTEOS is the quality of TEOS, in g; Vabsolute ethanol is the volume of absolute ethanol in mL; Vammonia is the volume of ammonia in mL 
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表 2 不同纤维膜的本征电阻与离子电导率
Table 2 Intrinsic resistance and ionic conductivity of different fiber membranes
Diaphragm type Diaphragm thickness /μm Body resistance/Ω Ionic conductivity/(mS·cm-1) Celgard 34.9 2.8 0.55 PES 188.5 2.12 3.92 PES/SiO2-0.5 203.5 2.33 3.85 PES/SiO2-1.0 211.3 2.61 3.57 PES/SiO2-1.5 188.9 2.73 3.05
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目的
锂离子电池因其高比能量密度、良好的循环性能及环境友好等特性，已广泛应用于电动汽车、电子产品和储能领域。然而，近年来锂离子电池在使用过程中频繁发生的安全事故，已引发对这一清洁能源安全性的广泛关注和质疑。本研究旨在制备一种结构纤维膜，通过结合静电纺丝法和原位生长法对纤维复合隔膜的结构进行优化，其中聚醚砜(PES)作为第一核层，二氧化硅(SiO)作为第二壳层。PES和SiO协同提供双重耐热骨架，分别作为耐热聚合物和无机骨架，共同支撑复合薄膜的结构，从而赋予其优异的耐热性。静电纺丝的PES纤维赋予膜优异的电解液亲和性，能够有效吸收并保留电解液。阻燃性能是电池安全性的关键，而耐热性则是阻燃性能发挥作用的基础。确保隔膜在高温下具有足够的尺寸稳定性，可以防止其在燃烧时发生收缩，从而使阻燃材料充分发挥作用。通过两者的协同作用，可开发出兼具高耐热性与高阻燃性的全新隔膜，用于制备更加安全的锂离子电池，从而有效应对锂电池的易燃易爆问题，显著提升其安全性能。
方法本研究通过配制PES纺丝液，利用静电纺丝法制备PES纤维膜，并在80 ℃条件下进行鼓风烘箱干燥处理。 之后通过原位生长技术，在PES纳米纤维表面包覆一层SiO，显著提升隔膜的力学性能和耐热稳定性。此外，高温灼烧下，SiO颗粒通过缩聚和交联形成Si—O—Si网状结构，有效阻断燃烧，从而赋予隔膜优异的阻燃性能。利用扫描电子显微镜(SEM)对复合隔膜的微观形貌进行分析，并采用傅里叶变换红外光谱(FTIR)对其微观结构进行表征。此外，通过X射线衍射仪对不同隔膜的结晶度进行测定。通过电化学稳定窗口、离子电导率、界面阻抗、循环性能及倍率性能测试，系统表征隔膜的电化学性能。同时，通过点火器灼烧试验，评估复合隔膜的阻燃性能。
结果通过微观形貌观察、隔膜微观结构分析以及X射线衍射(XRD)谱图的结果，验证了PES纤维膜上存在SiO。其中PES/SiO-1.5的吸液率超过商业Celgard隔膜的三倍。即使在200 ℃下，PES/SiO-1.5隔膜的结构和性能也未发生显著变化。PES/SiO-1.5隔膜的电化学稳定窗口高达5.45 V，离子电导率达到3.05 mS/cm，同时表现出优异的阻燃性能：在灼烧测试中，其尺寸保持稳定，并能在离火后迅速自熄。组装成全电池进行循环和倍率性能测试，在循环100次后，PES/SiO-1.5隔膜的容量保持率高达96.8%，并在倍率性能测试中展现出卓越的电化学性能。
结论本研究利用静电纺丝工艺制备PES纤维隔膜，并通过原位生长法在纤维表面包覆SiO，成功构筑出一种纤维复合隔膜，赋予其优异的阻燃性能。同时制备的纤维复合隔膜表现出卓越的耐热性能，在200 ℃下无明显收缩，灼烧测试中尺寸保持稳定，且离火后能够迅速自熄，为电池提供了可靠的安全保障。在三种复合隔膜中，PES/SiO-1.5纤维复合隔膜不仅具备出色的阻燃性能，同时还展现出优异的电化学性能。因此，该隔膜在提升大型锂离子电池的电化学性能和安全性方面展现出巨大的应用潜力。
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