聚醚侧链型聚硅氧烷对含氟聚合物凝胶锂离子电解质膜性能的影响

通过浸没沉淀相转化法制备了具有类似孔结构的聚醚侧链型聚硅氧烷(PDMS-g-(PPO-PEO))改性的聚偏氟乙烯(PVDF)和聚偏氟乙烯-六氟丙烯(PVDF-HFP)多孔骨架,经电解液活化后得到凝胶电解质膜,研究了PDMS-g-(PPO-PEO)对含氟聚合物凝胶电解质膜性能的影响。由改性PVDF和PVDF-HFP骨架被电解液活化制备的聚合物凝胶电解质膜,离子电导率分别达到2.2×10-3和1.7×10-3S/cm,综合分析凝胶电解质膜中电解液稳定性和膜的电化学性能发现,PDMS-g-(PPO-PEO)对PVDF骨架的改性效果明显优于PVDF-HFP骨架,共混改性后PVDF可代替PVDF-HFP作为隔膜作为锂离子电池凝胶电解质膜。     

溶胶-凝胶法制备微孔复合聚合物电解质

使用钛酸丁酯作为前驱体,在聚偏氟乙烯-六氟丙烯溶液中分解为T iO2,与聚合物基体进行复合,制备的聚合物膜吸附电解质溶液后成为微孔复合聚合物电解质(M CPE)。用SEM、DSC、FT-IR、XRD等方法对复合聚合物膜进行表征,并测试了M CPE的离子电导率,发现当复合聚合物膜中T iO2粒子的质量分数为8.2%时,聚合物电解质具有最高的离子电导率1.27×1-0 3S/cm。     

一种新型的复合离子液体的微孔聚合物电解质的制备与研究

利用相转化法制备了PVDF-HFP/PMMA的微孔聚合物膜,离子液体1-丁基-3-甲基咪唑四氟硼酸盐(BmimBF4)作为一种不易燃,不挥发性的增塑剂,用于活化微孔聚合物膜,最后得到一种安全的聚合物电解质。通过用场发射扫描电镜(FESEM)、离子液体载液量、孔隙率和差热分析(DSC)对由不同比例的PVDF-HFP/PMMA做成的微孔聚合物膜进行表面形貌及结构分析,并对得到的最优配比的微孔聚合物电解质的电化学性能进行了研究。研究结果表明:微孔聚合物电解质膜MIL-60表现出最低的玻璃化转变温度Tg以及在30℃下最高的离子电导率1.4×10-3S/cm,组装LiFePO4/MIL-60/Li扣式电池,在0.1C下首次放电可达到157mAh/g,并且在50次循环后还有151mAh/g。     

水性聚氨酯-聚二甲基硅氧烷共混体系聚合物电解质的研究

通过共混法,将不同质量分数的聚二甲基硅氧烷(PDMS)添加到水性聚氨酯(WPU)中,并加入适量锂盐(LiClO4)得到一系列聚合物电解质膜.测试结果表明,与WPU聚合物电解质相比,PDMS改性后的WPU聚合物电解质体系具有良好的热稳定性.将聚合物膜浸泡在1 mol/L LiClO4(PC)溶液中12h,可得到吸液率为119%凝胶聚合物电解质,其电导率在30℃时可达到1.01×10-3S/cm,80℃为5.17×10-3/cm.     

纳米SiO2/LiClO4/PVDF-HFP复合凝胶聚合物电解质的制备及其电化学性能

为了解决液态电解质锂离子电池存在的安全性问题,以偏氟乙烯和六氟丙烯的共聚物(PVDF-HFP)为基体,通过加入高氯酸锂(LiC1O4)、增塑剂(碳酸丙烯酯和碳酸二甲酯)、纳米二氧化硅等,制备出了具有高电导率的复合凝胶聚合物电解质.用X射线衍射仪测试聚合物电解质的结构,用交流阻抗法测定其电导率,用线性伏安扫描法研究了该聚合物电解质体系的电化学稳定性,并以其为电解质制备成锂离子电池进行充放电测试.结果表明,在20℃时复合凝胶聚合物电解质的电导率最高可达7.56×10-3S/cm,该电解质在4.6 V以下电化学窗口稳定,以其为电解质的锂离子电池具有良好的电化学性能,说明纳米SiO2/LiC1O4/PVDF-HFP复合凝胶聚合物电解质能满足锂离子电池的应用.     

直接挥发法制备无纺布增强型聚合物电解质

以N,N-二甲基-甲酰胺(DMF)为溶剂, 采用直接挥发法制备无纺布增强型聚偏氟乙烯-六氟丙烯(PVDF-HFP)聚合物电解质, 并以锂为负极制备了聚合物电池.用扫描电子显微镜、交流阻抗和循环伏安对所制聚合物膜性能进行了表征,用充放电实验对所制聚合物电池电化学性能进行了测试.实验结果表明,直接挥发法制得的聚合物膜孔穴丰富,微孔呈蜂窝状,吸液率为280%,电化学稳定窗口为4.5V,浸取电解液后室温离子电导率为1.5mS/cm;以LiCoO2为正极制得的聚合物电池0.1C充放电, 放电平台为3.9V左右, 首次放电容量为137.5mAh/g,20次循环后容量保持在134mAh/g以上,充放电库仑效率高于95%,0.5C放电时放电平台为3.7V,0.5和1C放电分别能保持0.1C放电容量的96%和93%.     

锂离子电池用固态偏氟乙烯-六氟丙烯共聚物电解质的研究进展

固体聚合物电解质具有质轻、安全、易加工等优点,在锂离子电池中具有极大的应用价值.综述了以偏氟乙烯-六氟丙烯(PVDF-HFP)共聚物为基的聚合物电解质的研究工作,介绍了PVDF-HFP固体电解质的制备方法,分析了影响此聚合物电解质性能的因素,并讨论了PVDF-HFP电解质的改性措施,对今后的发展方向作了简要展望.     

PVDF-HFP基聚合物电解质膜的制备及性能表征

采用相转化法制备了PVDF-HFP基多孔聚合物电解质,研究了PVDF-HFP的溶解温度、溶剂用量以及非溶剂用量等因素对聚合物电解质性能的影响,分别采用交流阻抗法和稳态电流法测定了聚合物电解质膜的离子电导率和离子迁移数,并通过扫描电镜观察了多孔聚合物膜的表面形貌.研究表明,制备PVDF-HFP多孔聚合物电解质膜的合适条件为:溶胶温度50~60℃、溶胶时间2 h、溶剂与PVDF的质量比为9~11、非溶剂与PVDF的质量比为0.5~0.25.该条件下制得的多孔聚合物电解质膜的孔隙率达到70%左右、离子迁移数在0.3左右、室温离子电导率达到1.6×10-3S.cm-1.     

改性SiO2/PVDF-HFP/PP无纺布复合膜的制备及电化学性能

利用γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(KH570)改性纳米SiO2(简称KH570@SiO2),与聚偏氟乙烯-六氟丙烯共聚物(PVDF-HFP)溶液混合,涂覆于聚丙烯(PP)无纺布上,制成KH570@SiO2/PVDF-HFP复合PP无纺布的锂离子电池隔膜。研究复合隔膜的物理性质,并分别与不含纳米SiO2的体系以及含未改性纳米SiO2的体系进行比较。通过扫描电子显微镜(SEM)、万能材料试验机、交流阻抗和充放电循环等测试,对复合隔膜的形态、力学性能和电化学性能等进行研究。结果表明,改性的纳米SiO2能够在复合隔膜中更好地分散,微孔更加均匀,而且复合隔膜的热性能和吸液率也有明显的提高。KH570@SiO2/PVDF-HFP/PP无纺布复合隔膜的离子电导率最高,可达1.5×10-3S/cm,组装的电池在0.2 C的充放电倍率下经过100次循环,放电比容量稳定,保持在146.6 mAh/g左右。     

热致相分离法制备聚偏氟乙烯-六氟丙烯多孔膜及其在聚合物锂离子电池中的应用

采用热致相分离技术成功制备出聚偏氟乙烯-六氟丙烯(PVDF-HFP))多孔膜,相图分析表明,PVDF-HFP/环丁砜体系发生固-液分相.SEM显示膜由球晶和丝状结晶组成.随聚合物浓度增加,多孔膜的结晶度、孔隙率以及平均孔径均降低,由多孔膜制得的凝胶聚合物电解质膜,其吸液率和电导率也降低,但多孔膜的力学性能提高.所有样品在20℃时的电导率超过2×100-3/cm,电化学窗口大于4.5 V.     

A lithium poly(pyromellitic acid borate) gel electrolyte membrane for lithium-ion batteries

Lithium poly(pyromellitic acid borate) (PPAB) was synthesized via polymerization of lithium tetramethanolatoborate and silylated pyromellitic acid. The synthesized material was characterized by Fourier transformation infrared spectroscopy, ¹¹B nuclear magnetic resonance, scanning electron microscopy, and thermogravimetric analysis. And electrochemical characterizations were carried out on the blended PPAB/PVDF-HFP membrane. The PPAB-based composite membrane exhibits high lithium ionic conductivity, a broad electrochemical window and a high lithium-ion transference number. The battery cells assembled with the PPAB/PVDF-HFP/EC:PC composite membrane as the electrolyte perform reasonably well not only at elevated temperature but also at room temperature with good cyclability and discharge capacity, making the material suitable for applications in lithium-ion batteries.     

PVDF-HFP基凝胶电解质用于LiNi0.5Co0.2Mn0.3O2三元正极锂离子电池

以聚偏氟乙烯-六氟丙烯(Poly(vinylidene fluoride-hexafluoropropylene),PVDF-HFP)为聚合物基体,新戊二醇二丙烯酸酯(Neopentyl glycol diacrylate,NPGDA)为交联剂,在引发剂偶氮二异丁腈(2,2′-Azobis(2-methylpropionitrile),AIBN)的作用下通过室温现场聚合法制备凝胶电解质用于锂离子电池。探索不同质量比PVDF-HFP/NPGDA对凝胶电解质性能和LiNi_(0.5)-Co_(0.2)Mn_(0.3)O_2三元正极锂离子电池性能的影响。结果表明,当质量比为1∶1时,凝胶电解质具有较高的离子电导率,为8.45mS·cm~(-1),锂离子迁移数为0.78,电化学窗口为4.5V。在电流密度30mA·g~(-1)恒流充放电,首次放电比容量为143mAh·g~(-1),循环50次后仍高达135.3mAh·g~(-1)。电流密度为300mA·g~(-1)时,放电比容量为100.2mAh·g~(-1)。     

Boosting Thermal and Mechanical Properties: Achieving High-Safety Separator Chemically Bonded with Nano TiN Particles for High Performance Lithium-Ion Batteries

Currently, the commercial separator (Celgard2500) of lithium-ion batteries (LIBs) suffers from poor electrolyte affinity, mechanical property and thermal stability, which seriously affect the electrochemical performances and safety of LIBs. Here, the composite separators named PVDF-HFP/TiN for high-safety LIBs are synthesized. The integration of PVDF-HFP and TiN forms porous structure with a uniform and rich organic framework. TiN significantly improves the adsorption between PVDF-HFP and electrolyte, causing a higher electrolyte absorption rate (192%). Meanwhile, XPS results further demonstrate the tight link between PVDF-HFP and TiN due to the existence of Ti F bond in PVDF-HFP/TiN, resulting in a strong impediment for the puncture of lithium dendrites as a result of the improved mechanical strengths. And PVDF-HFP/TiN can effectively suppress the growth of lithium dendrites by means of uniform lithium flux. In addition, the excellent heat resistance of TiN improves the thermal stability of PVDF-HFP/TiN. As a result, the LiFePO₄||Li cells assembled PVDF-HFP/TiN-12 exhibit excellent specific capacity, rate performance, and capacity retention rate. Even the high specific capacity of 153 mAh g⁻¹ can be obtained at the high temperature of 80 °C. Meaningfully, a reliable modification strategy for the preparation of separators with high safety and electrochemical performance in LIBs is provided.     

干法制备聚合物锂离子电池用PVDF-HFP隔膜的研究

采用相转化法(干法)以PVDF-HFP(聚偏氟乙烯-六氟丙烯共聚物)为本体聚合物制备了聚合物锂离子电池用隔膜.通过扫描电镜对隔膜形貌进行分析,研究了在干法制膜过程中空气湿度对隔膜形貌和性质的影响.采用交流阻抗技术和PC(碳酸丙烯酯)浸入实验分别测定了隔膜的电导率和吸液率.采用吸液率最高,相对湿度50%下制备的隔膜装配电池,测其电化学性质.电池首次充放电效率为88.3%,第五周可达99.4%,表现出良好的电化学性能.     

后处理工艺对POSS-PMMA_8改性凝胶聚合物电解质性能的影响

为解决凝胶聚合物电解质(GPE)的离子电导率低、力学性能差等问题,通过静电纺丝制备星型笼型低聚倍半硅氧烷-聚甲基丙烯酸甲酯(POSS-PMMA_8)改性聚甲基丙烯酸甲酯-聚丙烯腈-聚偏氟乙烯(PMMA-PANPVDF)得到聚合物纺丝薄膜(POSS-PMMA_8/PMMA-PAN-PVDF)M1,将聚合物纺丝薄膜M1在120℃热处理得到聚合物纺丝薄膜M2,或热压并预氧化处理得到聚合物纺丝薄膜M3,将其浸泡于电解液中活化得到POSS-PMMA_8/PMMA-PAN-PVDF的GPE。对不同状态聚合物纺丝薄膜M1、M2、M3的形貌、孔隙率、吸液率、力学性能及其GPE的电导率和电化学稳定窗口进行测试。结果发现,相比于M1,M2的拉伸强度及GPE的电导率分别提高9.2%及181.1%,电化学窗口增至5.3 V;而M3的拉伸强度和GPE电导率分别较M1增加193.7%、20.2%,电化学窗口增至5.5V。     

Performance characteristics of guanine incorporated PVDF-HFP/PEO polymer blend electrolytes with binary iodide salts for dye-sensitized solar cells

In this work, we have investigated the influence of guanine as an organic dopant in dye-sensitized solar cell (DSSC) based on poly(vinylidinefluoride-co-hexafluoropropylene) (PVDF-HFP)/polyethylene oxide (PEO) polymer blend electrolyte along with binary iodide salts (potassium iodide (KI) and tetrabutylammonium iodide (TBAI)) and iodine (I₂). The PVDF-HFP/KI + TBAI/I₂, PVDF-HFP/PEO/KI + TBAI/I₂ and guanine incorporated PVDF-HFP/PEO/KI + TBAI/I₂ electrolytes were prepared by solution casting technique using DMF as solvent. The PVDF-HFP/KI + TBAI/I₂ electrolyte showed an ionic conductivity value of 9.99 × 10⁻⁵ Scm⁻¹, whereas, it was found to be increased to 4.53 × 10⁻⁵ Scm⁻¹ when PEO was blended with PVDF-HFP/KI + TBAI/I₂ electrolyte. However, a maximum ionic conductivity value of 3.67 × 10⁻⁴ Scm⁻¹ was obtained for guanine incorporated PVDF-HFP/PEO/KI + TBAI/I₂ blend electrolyte. The photovoltaic properties of all these polymer electrolytes in DSSCs were characterized. As a consequence, the power conversion efficiency of the guanine incorporated PVDF-HFP/PEO/KI + TBAI/I₂ electrolyte based DSSC was significantly improved to 4.98% compared with PVDF-HFP/PEO/KI + TBAI/I₂ electrolyte based DSSC (2.46%). These results revealed that the guanine can be an effective organic dopant to enhance the performance of DSSCs.     

Influence of Finely Dispersed Carbon Nanotubes on the Performance Characteristics of Polymer Electrolytes for Lithium Batteries

Electrospun membranes of poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP)/multiwall carbon nanotube (MWCNT) composite are prepared and loaded with lithium salts from electrolyte solution. Field emission transmission electron microscopy provides evidence for the uniform distribution of MWCNTs into the matrix of PVdF-HFP. The interconnected morphology as evident from field emission scanning electron micrograph forms the path for the lithium ion conduction. Results from electrochemical impedance spectroscopy inform that the presence of MWCNTs in PVdF-HFP matrix improves interfacial stability between lithium electrode and membrane and augment conduction path in the polymer electrolyte membrane. Further results from impedance measurement reveal the contribution of MWCNTs toward conductivity. A prototype cell is fabricated with PVdF-HFP/MWCNT as polymer electrolyte. The electrospun PVdF-HFP electrolyte membrane with 2% MWCNTs content shows an ionic conductivity of about 5.85 mSmiddotcm^-1 at 25 degC. Also, PVdF-HFP/MWCNT electrolyte membrane exhibits good electrochemical and interfacial stability and can be potentially suitable as electrolyte in lithium ion secondary battery     

Poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP) membranes for ethyl acetate removal from water

In this study, poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP) with low crystallinity was applied as the membrane material for pervaporative separating ethyl acetate (EtAc) from its aqueous solutions. The drying conditions during membrane fabrication by means of casting the PVDF-HFP solution dominated the obtained membrane morphologies when the polar solvents such as dimethylacetamide (DMAc) and acetone were used. It was demonstrated that both the DMAc-cast and acetone-cast PVDF-HFP membranes vacuum-dried at 60 degrees C were dense but had different crystalline structures. Predominantly alpha and gamma crystalline phases were found in the acetone-cast and DMAc-cast PVDF-HFP membranes, respectively. And the different pervaporative separating performances of the two solvent-cast PVDF-HFP membranes were well explained in terms of different solution-diffusion properties which were induced from the permeants/polymer interactions on the base of the polarity differences between permeants and the two solvent-cast PVDF-HFP membranes.     

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

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%。