大倍率高耐热聚醚酰亚胺-聚偏氟乙烯芯壳纳米纤维锂离子电池隔膜

以高耐热、高强度的聚醚酰亚胺（PEI）为芯层材料,以电解液亲和性和界面稳定性优良的聚偏氟乙烯（PVDF）为壳层材料,构建了一种具有同轴结构的大倍率、高耐热PEI-PVDF纳米纤维锂离子电池隔膜。通过SEM、TEM、TGA、电化学工作站、电池测试系统对PEI-PVDF同轴隔膜的微观形貌和性能进行测试与表征。结果表明:PEI-PVDF同轴纤维具有清晰的芯壳结构,与商业隔膜相比,PEI-PVDF同轴隔膜具有优异的热稳定性,在180℃下处理2 h,尺寸稳定并未发生热收缩;吸液率达到520%;电化学稳定性优异,电化学窗口达到5.0 V;离子电导率达到2.3 mS·cm-1;采用PEI-PVDF隔膜组装的锂离子电池在8 C的放电流下放电比容量仍能达到107 mAh·g-1,再回到0.2 C时恢复到原始比容量的95.4%,且电池在1 C电流下循环100次后容量保持率高达92.5%,PEI-PVDF隔膜表现出的大倍率、高耐热的特点说明该纤维膜是一种高功率、高安全的锂离子电池隔膜。      

聚偏氟乙烯-沸石复合锂电隔膜的制备及性能

针对传统聚烯烃类锂离子电池隔膜的耐温性差和电解液亲和性差的问题,本实验以微孔沸石纳米粒子和聚偏氟乙烯树脂(PVDF)为主要原料,通过相转化法制备了综合性能优异的沸石/PVDF复合锂电隔膜。结果表明:与商用聚乙烯(PE)膜相比,所制备的沸石/PVDF复合隔膜具有更加发达的孔道结构,其孔隙率超过70%,约为PE膜的2倍。沸石/PVDF复合膜的耐高温性和电解液润湿性明显优于PE膜和纯PVDF膜,经过160℃、0.5h的高温处理后,复合膜的热收缩率仅为5%,而PE膜已完全融化,收缩率达到100%,PVDF膜收缩率超过50%;沸石/PVDF复合膜的电解液接触角仅为7.4°,而PE膜和PVDF膜的接触角高达42.5°和31.7°。受益于丰富的孔道结构和良好的电解液吸收/保持能力,沸石/PVDF复合膜所装配锂离子电池的倍率放电容量高于PE膜,同时,该复合膜装配电池的循环性能也优于传统聚乙烃隔膜。     

Preparation and performance of silica/polypropylene composite separator for lithium-ion batteries

In an effort to improve thermal stability and mechanical properties of porous polypropylene (PP) separators for lithium-ion battery, SiO₂/PP/SiO₂ composite separators were prepared by introducing SiO₂ layer on both sides of PP separator through a dip-coating process, with polyvinylidene fluoride–hexafluoropropylene (PVDF–HFP) as binder. SiO₂ nanoparticles are evenly distributed and closely packed in the coated layer, which features a porous honeycomb structure. This unique porous structure was quantitatively analyzed by Gurley value, and it can retain liquid electrolyte, leading to higher electrolyte uptake and ionic conductivity of the composite separator. The introduction of SiO₂-coated layers can not only suppress thermal shrinkage but also improve mechanical properties of the composite separator. C-rate capability and cycle performance of composite separator were also investigated, and compared to those of pristine PP separator.     

Preparation of poly(vinyl alcohol)-based separator with pore-forming additive for lithium-ion batteries

In this work, poly(vinyl alcohol) (PVA)-based separators with microporous structure were prepared from a casting solution composed of PVA resin, water as solvent, and poly(vinyl pyrrolidone) (PVP) polymer as pore controlling additive by non-solvent induced phase separation (NIPS) wet-process and investigated in lithium-ion batteries. The effects of PVP on the morphology and properties of the separator, such as porosity, electrolyte wettability, thermal stability and battery performance (discharge capacity, C-rate capability and cycleability) were systematically analyzed. Results show that PVP induced more pores on the bottom surfaces and the electrolyte uptake, ionic conductivity was further improved. Finally, a 10 wt% PVA-based separator with PVP solid content of 6 wt% exhibited greatly improved porosity, electrolyte uptake, ion conductivity and thermal resistance, resulting in the cell with high safety performance and matched electrochemical performance. The results demonstrated that the PVA-based separator with PVP as pore controlling additive can be a successful candidate serving as an effective separator for lithium-ion battery. Additionally, the present method of producing the microporous separator for LIBs is simple, environmentally benign and economically viable.     

静电纺丝与静电喷雾技术共纺制备PPESK/PVDF复合锂电池隔膜

为了改善传统静电纺丝无纺布纤维膜力学性能较差的缺点,采用静电纺丝和静电喷雾技术相结合的方法,同时进行静电纺PPESK浓溶液和PVDF稀溶液,制备得到PPESK纤维/PVDF珠粒复合锂电池隔膜,并在160℃进行热压后处理。通过扫描电子显微镜、万能拉伸试验机、电化学工作站及充放电测试仪等表征复合锂电池隔膜的微观结构、力学性能、离子电导率和相应的电池充放电性能。结果表明,该复合隔膜具有良好的电解液润湿性,室温下离子电导率达到1.92mS·cm^-1,PVDF珠粒均匀地分布在PPESK纤维中,珠粒经热压产生微熔融有效增强了纤维之间的黏结力,使复合膜的力学强度提高到13.2MPa。此外,使用复合隔膜装配的电池展现出较高的放电比容量和稳定的循环性能。     

Electrochemical studies on polymer electrolytes based on poly(vinylidene fluoride-co-hexafluoropropylene) membranes prepared by electrospinning and phase inversion—A comparative study

The synthesis, characterization and electrochemical properties of poly(vinylidene fluoride-co-hexafluoropropylene) {P(VdF-co-HFP)} prepared by electrospinning and phase inversion methods are reported. The morphologies of the membranes were studied by field emission scanning electron microscope and atomic force microscope. Thermal properties of the membranes were evaluated by differential scanning calorimetry. The resultant porous membranes are good absorbents of liquid electrolytes and exhibit high electrolyte retention capacity. The polymer electrolytes were prepared by soaking the membranes in liquid electrolyte. The temperature dependent ionic conductivity and electrochemical properties were evaluated. Li/LiFePO₄ cell with electrospun membrane delivers a discharge capacity of 145 mAh/g, which corresponds to 85% utilization of active material under the test conditions and shows lower capacity fade under continuous cycling.     

无机涂层改善锂离子电池聚烯烃隔膜性能研究

为了提高锂离子电池用聚烯烃微孔膜的综合性能, 在商用Celgard膜表面涂布ZrO₂无机涂层, 粘结剂选用电池用聚偏氟乙烯。对比分析涂覆前后的隔膜发现, ZrO₂涂层可以显著提高Celgard膜的热尺寸稳定性和热熔化温度, 对提高锂离子电池安全性起到积极作用。同时无机涂层还能明显改善隔膜对电解液的浸润性, 复合隔膜具有更好的保液能力, 以涂有ZrO₂涂层的Celgard膜作为隔膜组装锂离子电池,可以显著提高长期充放电循环时电池容量保持率。     

锂离子电池用PVDF/P(MMA-co-DMAEMA)共混隔膜的制备与性能

首先合成了甲基丙烯酸甲酯(MMA)与甲基丙烯酸-N,N-二甲胺乙酯的共聚物P(MMA-co-DMAE-MA),与聚偏氟乙烯(PVDF)共混经溶液相转化法制备了PVDF/P(MMA-co-DMAEMA)隔膜。研究发现,相对于纯PVDF隔膜,共混隔膜的孔隙率增加,结晶度降低,电解液吸收稳定性显著提高。共混隔膜具有"活性"隔膜的性质,隔膜-电解液组成的电解质体系表现出凝胶电解质特征,隔膜中PVDF/P(MMA-co-DMAE-MA)质量比为10/1时,隔膜吸液率在420%以上,活化后凝胶电解质膜离子电导率可达到1.8×10-3S/cm。研究结果表明,采用溶液相转化法制备PVDF/P(MMA-co-DMAEMA)共混隔膜,是一种制备凝胶锂离子电池用高性能活性隔膜的有效方法。     

Electrochemical performances and thermal properties of electrospun Poly(phthalazinone ether sulfone ketone) membrane for lithium-ion battery

A novel Poly(phthalazinone ether sulfone ketone) (PPESK) membrane for lithium-ion battery was prepared using electrospinning technique. The morphology, electrochemical performances and thermal properties of electrospun PPESK fabrics were investigated. Results indicate that electrospun PPESK fabrics have high porosity of 92% and high electrolyte uptake of 1210%, which lead to their high ionic conductivity of 3.79 × 10^− 3 S·cm^− 1 at 25 °C. The cell assembled with PPESK fabrics displays better electrochemical stability and higher cycling discharge capacity than that assembled with PVDF fabrics. Moreover, electrospun PPESK fabrics exhibit excellent thermal dimensional stability. When PPESK fabrics are treated in oven at 220 °C for 1 h, the shape of membrane is unchanged. Electrospun PPESK fabrics have possible applications for high performance lithium-ion battery.     

聚硅氧烷/聚苯硫醚无纺布复合电池隔膜的制备与性能

以聚乙烯基硅氧烷（PVS）为涂覆材料,以耐高温聚苯硫醚（PPS）无纺布为支撑材料,通过物理浸涂的方法制备了PVS/PPS无纺布复合锂离子电池隔膜。通过对基本物理性能、电化学性能和电池性能的系统考察,发现与聚烯烃（PP/PE/PP）隔膜相比,PVS/PPS复合隔膜具有较发达的微孔结构、良好的润湿性、较高的离子电导率及良好的界面相容性,有助于降低电池工作时的欧姆极化程度,并使电池表现出较高的放电比容量和良好的循环稳定性（保持率约为100%）。此外研究发现,PVS/PPS复合隔膜具有优异的耐热性,在250℃的高温下热处理1 h后仍能表现出较好的尺寸稳定性。可见,PPS无纺布基复合隔膜在动力型锂离子电池领域具有很大的发展前景。      

Flexible,High‐Wettability and Fire‐Resistant Separators Based on Hydroxyapatite Nanowires for Advanced Lithium‐Ion Batteries

Separators play a pivotal role in the electrochemical performance and safety of lithium‐ion batteries (LIBs). The commercial microporous polyolefin‐based separators often suffer from inferior electrolyte wettability, low thermal stability, and severe safety concerns. Herein, a novel kind of highly flexible and porous separator based on hydroxyapatite nanowires (HAP NWs) with excellent thermal stability, fire resistance, and superior electrolyte wettability is reported. A hierarchical cross‐linked network structure forms between HAP NWs and cellulose fibers (CFs) via hybridization, which endows the separator with high flexibility and robust mechanical strength. The high thermal stability of HAP NW networks enables the separator to preserve its structural integrity at temperatures as high as 700 °C, and the fire‐resistant property of HAP NWs ensures high safety of the battery. In particular, benefiting from its unique composition and highly porous structure, the as‐prepared HAP/CF separator exhibits near zero contact angle with the liquid electrolyte and high electrolyte uptake of 253%, indicating superior electrolyte wettability compared with the commercial polyolefin separator. The as‐prepared HAP/CF separator has unique advantages of superior electrolyte wettability, mechanical robustness, high thermal stability, and fire resistance, thus, is promising as a new kind of separator for advanced LIBs with enhanced performance and high safety.     

Polypyrrole/poly(vinyl alcohol-co-ethylene) nanofiber composites on polyethylene terephthalate substrate as flexible electric heating elements

Polypyrrole/poly(vinyl alcohol-co-ethylene) (PPy/PVA-co-PE) nanofiber composites on polyethylene terephthalate (PET) substrates were prepared using spray coating technique and in situ polymerization process. The electric heating behaviors of composites were investigated as functions of the amounts of nanofiber and PPy. It was observed that, the electrical resistivity of composites decreased significantly with increasing nanofiber and PPy contents. Scanning electron microscope images and infrared spectrum studies confirmed the formation of well dispersed network-like structure of PPy/PVA-co-PE nanofibers on PET substrate. Furthermore, maximum temperature attained at a given applied voltage for the composites could be well controlled by changing nanofibers and PPy amounts. PPy/PVA-co-PE nanofiber/PET composites exhibited excellent electric heating performance in aspects of rapid temperature response, long retaining behavior, thermal and operational stability. The incorporation of PPy on PVA-co-PE nanofibers/PET nonwoven substrates resulted in high conductivity and enhanced heating behavior, which have potential to be used as efficient electric heating elements.     

质子传导膜制备方法放大与膜性能表征

为了满足新能源电池对质子选择性导电膜的需要,提出一种质子传导膜的新型制备工艺,并进行质子传导膜的制备工艺放大.以聚偏氟乙烯(PVDF)和烯丙基磺酸钠(SAS)为原料,成功制备长1 000mm、宽800mm的质子传导膜.膜性能测试结果显示,质子传导膜电导率随SAS质量分数变化显著.当SAS质量分数为20%时,膜电导率3.0×10-2 S/cm;膜化学稳定性良好,使用Fenton试剂氧化法测得膜剩余质量分数97.5%;屈服强度23N/mm2,膜爆破强度为2MPa;TGA分析膜分解温度高于400℃.该膜应用于全钒液流电池,自放电实验测得开路电压下降速率为1.41×10-3 V/h,库伦效率93%.结果表明,膜材料综合性能良好,有望在全钒液流电池产业化过程中得到大规模应用.     

静电纺丝聚芳醚砜酮纤维膜穿刺强度研究

静电纺丝纤维膜因为具有高孔隙率、大的比表面积和良好的电解液润湿性而被广泛地应用于锂离子电池隔膜的研究,但对于锂离子电池安全性能至关重要的隔膜穿刺强度的研究还比较匮乏。本工作采用静电纺丝技术制备得到PPESK纤维膜,并采用热处理提高纤维膜的力学性能,然后通过穿刺实验测得一系列不同厚度热处理PPESK纤维膜的穿刺强度,并建立起穿刺强度与纤维膜厚度之间的线性关系。通过对穿刺破坏区域的微观分析,探究热处理PPESK纤维膜穿刺破坏机理,结果表明:各向同性的热处理PPESK纤维膜穿刺过程是由纤维受挤压产生弯曲、变形和断裂造成的破坏,破坏区域呈近似圆形穿刺孔,而PP微孔膜的破坏区域则是由脆性断裂造成的长条形裂缝,相比之下热处理PPESK纤维膜的穿刺破坏过程更加缓和,可以降低锂枝晶刺穿隔膜带来的风险,但是热处理PPESK纤维膜的穿刺强度还有待增强。     

Research on hydrophobicity of electrospun Fe3O4/PVDF nanofiber membranes under different preparation conditions

Abstract

Preparation condition can affect the structure and the properties of nanofiber membrane. In order to explore suitable conditions to prepare the Fe₃O₄/PVDF nanofiber membrane with good hydrophobicity, the hydrophobicity of Fe₃O₄/PVDF nanofiber membranes obtained by electrospinning was investigated by changing preparation conditions like weight percentage of Fe₃O₄ nanoparticles, blending quality concentration of poly (vinylidene fluoride) (PVDF) and Fe₃O₄ nanoparticles, and positive voltage. And the variations of hydrophobicity of Fe₃O₄/PVDF nanofiber membranes modified by 1H, 1H, 2H, 2H-perfluorodecyl trimethoxysilane were studied. The results show that the hydrophobicity of Fe₃O₄/PVDF nanofiber membranes has changed under different preparation conditions. The contact angles of samples increased after a modification by 1H, 1H, 2H, 2H-perfluorodecyl trimethoxysilane, which indicates that the hydrophobicity of Fe₃O₄/PVDF nanofiber membranes has been enhanced.     

Electrospun nanofibrous biodegradable polyester coatings on Bioglass-based glass-ceramics for tissue engineering

Biodegradable polymeric nanofibrous coatings were obtained by electrospinning different polymers onto sintered 45S5 Bioglass^®-based glass-ceramic pellets. The investigated polymers were poly(3-hydroxybutyrate) (P3HB), poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) and a composite of poly(caprolactone) (PCL) and poly(ethylene oxide) (PEO) (PCL–PEO). The fibrous coatings morphology was evaluated by optical microscopy and scanning electron microscopy. The electrospinning process parameters were optimised to obtain reproducible coatings formed by a thin web of polymer nanofibres. In-vitro studies in simulated body fluid (SBF) were performed to investigate the bioactivity and mineralisation of the substrates by inducing the formation of hydroxyapatite (HA) on the nanofiber-coated pellets. HA crystals were detected on all samples after 7 days of immersion in SBF, however the morphology of the HA layer depended on the characteristic fibre diameter, which in turn was a function of the specific polymer-solvent system used. The bioactive and resorbable nanofibrous coatings can be used to tailor the surface topography of bioactive glass-ceramics for applications in tissue engineering scaffolds.     

SiO2/sulfonated poly ether ether ketone (SPEEK) composite nanofiber mat supported proton exchange membranes for fuel cells

A composite membrane of silica (SiO₂)/sulfonated poly (ether ether ketone) (SPEEK) nanofiber mat impregnated with Nafion was fabricated and evaluated for its potential use as a proton conductor for high temperature polymer electrolyte membrane fuel cells. The supporting SiO₂/SPEEK composite nanofibrous skeleton was prepared via electrospinning of a mixture of SPEEK solution and silica sol prepared from tetraethyl orthosilicate (TEOS). The control of hydrolysis and condensation of TEOS enabled to form entangled SiO₂ networks miscible to SPEEK solution. The prepared SiO₂/SPEEK nanofiber mat was impregnated with Nafion^® to completely fill the inter-fiber voids to prepare a dense membrane. The morphology of the nanofiber mat and the composite membrane were observed by scanning electron microscopy and the presence of SiO₂ and SPEEK in the prepared nanofibers was confirmed by FTIR spectroscopy. Proton conductivity and swelling of the membrane were measured. The H₂/O₂ single cell test using the composite membrane as a PEM was performed. At a high temperature and low humidity condition (120 °C and 40 % RH), the maximum power density was 170 mW/cm² for the Nafion-impregnated SiO₂/SPEEK (40/60 w/w) composite nanofiber membrane that was 2.4 times higher than recast Nafion (71 mW/cm²) while SPEEK film failed.     

Templated synthesis of porous TiO2 thin films using amphiphilic graft copolymer and their use in dye-sensitized solar cells

Porous TiO₂ thin films have been prepared using an amphiphilic graft copolymer, i.e. poly(vinylidene fluoride-co-chlorotrifluoroethylene)-graft-poly(oxyethylene methacrylate) (P(VDF-co-CTFE)-g-POEM) as a structure-directing agent via the sol-gel process. The graft copolymer was synthesized via atom transfer radical polymerization using CTFE units as an initiating site and designed to have a hydrophobic P(VDF-co-CTFE) domain and a hydrophilic POEM domain. Fourier transform-infra red spectroscopy indicated that a hydrophilic titania precursor was selectively incorporated into hydrophilic POEM domains. In-situ formation and morphologies of porous TiO₂ thin films were confirmed by ultraviolet-visible spectroscopy, X-ray diffraction, transmission electron microscopy and thermogravimetric analysis. The resultant porous TiO₂ films with 10-25 nm in size were used as a photoelectrode for solid-state dye-sensitized solar cells, exhibiting energy conversion efficiency of 2.8% at 100 mW/cm².     

勃姆石纳米片增强锂离子电池隔膜性能研究

采用勃姆石涂覆改性聚烯烃隔膜可以提升锂离子电池的隔膜热稳定性和电解液润湿性。本工作通过简单的水热法合成了平均粒径约为150 nm的勃姆石纳米片, 并采用刮涂法涂覆在聚乙烯(Polyethylene, PE)隔膜表面。该涂覆隔膜的孔隙率达到46.6%、吸液率为138.9%、离子电导率为0.47 mS/cm和锂离子迁移数为0.42, 使得该隔膜组装的锂离子电池具有较好的循环稳定性, 在1C(1C=150 mA/g)的电流密度下循环100次后仍能保留93.7%的放电比容量。同时, 勃姆石纳米片涂覆的隔膜的孔结构分布均匀, 优化了锂离子传输通量, 抑制了锂枝晶。     

Dual‐Layer Superamphiphobic/Superhydrophobic‐Oleophilic Nanofibrous Membranes with Unidirectional Oil‐Transport Ability and Strengthened Oil–Water Separation Performance

Thin porous membranes with unidirectional oil‐transport capacity offer great opportunities for intelligent manipulation of oil fluids and development of advanced membrane technologies. However, directional oil‐transport membranes and their unique membrane properties have seldom been reported in research literature. Here, it is proven that a dual‐layer nanofibrous membrane comprising a layer of superamphiphobic nanofibers and a layer of superhydrophobic oleophilic nanofibers has an unexpected directional oil‐transport ability, but is highly superhydrophobic to liquid water. This novel fibrous membrane is prepared by a layered electrospinning technique using poly(vinylidene fluoride‐hexafluoropropylene) (PVDF‐HFP), PVDP‐HFP containing well‐dispersed FD‐POSS (fluorinated decyl polyhedral oligomeric silsesquioxanes), and FAS (fluorinated alkyl silane) as materials. The directional oil‐transport is selective only to oil fluids with a surface tension in the range of 23.8–34.0 mN m^–1. By using a mixture of diesel and water, it is further proven that this dual‐layer nanofibrous membrane has a higher diesel–water separation ability than the single‐layer nanofiber membranes. This novel nanofibrous membrane and the incredible oil‐transport ability may lead to the development of intelligent membrane materials and advanced oil–water separation technologies for diverse applications in daily life and industry.