Morphology and ionic conductivity of thermoplastic polyurethane electrolytes

Thermoplastic polyurethane (TPU) with a mixture of soft segments [poly(ethylene glycol) (PEG) and poly(tetramethylene glycol) (PTMG)], denoted TPU‐M, was prepared as an ion‐conducting polymer electrolyte. TPUs with PEG and PTMG as soft segments were also synthesized individually as polymer electrolytes. The changes in the morphology and ion conductivity of the phase‐segregated TPU‐based polymer electrolytes as a function of the lithium perchlorate concentration were determined with differential scanning calorimetry, Fourier transform infrared spectroscopy, alternating‐current impedance, and linear sweep voltammetry measurements. Both solid and gelatinous polymer electrolytes were characterized in this study. The effect of temperature on conductivity was studied. The conductivity changes revealed the combined influence of PTMG and PEG units in TPU‐M. The swelling characteristics in a liquid electrolyte and the dimensional stability were evaluated for the three TPUs. Because of its dimensional stability and ionic conductivity, the TPU system containing both PEG and PTMG as soft segments was found to be more suitable for electrolyte applications. A room‐temperature conductivity of approximately 1 × 10^?4 was found for TPU‐M containing 50 wt % liquid electrolyte. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1154–1167, 2004     

单离子型全氟凝胶聚合物固体电解质的结构与离子导电性能

从Nafion树脂出发,制备了一系列单离子型全氟凝胶聚合物固体电解质膜,其中有机极性介质为碳酸丙烯酯(PC)。通过溶胀曲线测定、红外光谱分析、复阻抗分析等手段对材料的结构与离子导电性能进行了研究。结果表明,PC与阳离子之间存在较强的相互作用,而且PC与Li+离子之间的相互作用强于PC与H+离子之间的相互作用。PC含量对材料的离子导电性能也有较大的影响。随着PC含量的增加,材料的离子电导率呈上升趋势。当PC含量较低时,Li+型样品的室温离子电导率高于H+型样品;而PC含量较高时,Li+型样品的室温离子电导率则低于H+型样品。Li+型样品和H+型样品的室温离子电导率均可达到1.25×10-4S·cm-1。     

苯酐改性聚乙二醇型聚氨酯固态电解质的制备与性能

以异佛尔酮二异氰酸酯（IPDI）、聚对苯二甲酸-3-甲基-1,5-戊二醇酯二醇（TPA-1000）、聚乙二醇（PEG-2000）、一缩二乙二醇（DEG）为主要原料合成了一系列热塑型聚氨酯弹性体,然后加入20%的锂盐（LiTFSI）制备不同的全固态电解质（SPE）。结果表明,随着TPA-1000含量的减少和PEG-2000含量的增加,SPE的耐热性增加,玻璃化转变温度减小,拉伸强度减小,断裂伸长率增加。SPE的离子电导率与温度的关系基本符合Arrhenius方程,在80℃,SPE（除纯PEG-2000的电解质外）的电化学窗口均达到4.0V以上,其中质量比TPA-1000：PEG-2000=1：2（SPE4）综合性能最佳,力学为1.87Mpa、电导率为2.15?10-4 S cm-1、窗口为4.3V。以SPE4组装的全固态电池在80℃、0.2C下放电比容量为150 mAh/g。     

Composite polymer electrolytes based on electrospun thermoplastic polyurethane membrane and polyethylene oxide for all‐solid‐state lithium batteries

To improve the electrochemical properties and enhance the mechanical strength of solid polymer electrolytes, series of composite polymer electrolytes (CPEs) were fabricated with hybrids of thermoplastic polyurethane (TPU) electrospun membrane, polyethylene oxide (PEO), SiO₂ nanoparticles and lithium bis(trifluoromethane)sulfonamide (LiTFSI). The structure and properties of the CPEs were confirmed by SEM, XRD, DSC, TGA, electrochemical impedance spectroscopy and linear sweep voltammetry. The TPU electrospun membrane as the skeleton can improve the mechanical properties of the CPEs. In addition, SiO₂ particles can suppress the crystallization of PEO. The results show that the TPU‐electrospun‐membrane‐supported PEO electrolyte with 5 wt% SiO₂ and 20 wt% LiTFSI (TPU/PEO‐5%SiO₂‐20%Li) presents an ionic conductivity of 6.1 × 10^?4 S cm^?1 at 60 °C with a high tensile strength of 25.6 MPa. The battery using TPU/PEO‐5%SiO₂‐20%Li as solid electrolyte and LiFePO₄ as cathode shows an attractive discharge capacity of 152, 150, 121, 75, 55 and 26 mA h g^?1 at C‐rates of 0.2C, 0.5C, 1C, 2C, 3C and 5C, respectively. The discharge capacity of the cell remains 110 mA h g^?1 after 100 cycles at 1C at 60 °C (with a capacity retention of 91%). All the results indicate that this CPE can be applied to all‐solid‐state rechargeable lithium batteries. © 2018 Society of Chemical Industry     

Preparation and characterization of novel hybrid thermoplastic poly(ether urethane)/poly(vinylidene fluoride) elastomers,and their application as solid polymer electrolytes

A comb‐like polyether, poly(3‐2‐[2‐(2‐methoxyethoxy)ethoxy]ethoxymethyl‐3′‐methyloxetane) (PMEOX), was reacted with hexamethylene diisocyanate and extended with butanediol in a one‐pot procedure to give novel thermoplastic elastomeric poly(ether urethane)s (TPEUs). The corresponding hybrid solid polymer electrolytes were fabricated through doping a mixture of TPEU and poly(vinylidene fluoride) with three kinds of lithium salts, LiClO₄, LiBF₄ and lithium trifluoromethanesulfonimide (LiTFSI), and were characterized using differential scanning calorimetry, thermogravimetric analysis and Fourier transform infrared spectroscopy. The ionic conductivity of the resulting polymer electrolytes was then assessed by means of AC impedance measurements, which reached 2.1 × 10^?4 S cm^?1 at 30 °C and 1.7 × 10^?3 S cm^?1 at 80 °C when LiTFSI was added at a ratio of O:Li = 20. These values can be further increased to 3.5 × 10^?4 S cm^?1 at 30 °C and 2.2 × 10^?3 S cm^?1 at 80 °C by introducing nanosized SiO₂ particles into the polymer electrolytes. Copyright © 2006 Society of Chemical Industry     

Soft segmental effect of methylene bis(p‐cyclohexyl isocyanate) based thermoplastic polyurethane impregnated with lithium perchlorate/propylene carbonate on ionic conductivity

Thermoplastic polyurethane (TPU) was employed as the polymer matrix for ion conduction as gelled electrolytes with lithium perchlorate (LiClO₄) in propylene carbonate (PC) solution. The TPU was prepared by methylene bis(p‐cyclohexyl isocyanate) as the hard segment while employing both poly(ethylene glycol) (PEG) and poly(tetramethylene glycol) (PTMG) as the soft segments. The copolymer comprising both PEG and PTMG was prepared such that it possessed the combined characteristics of good conductivity from the former and good mechanical properties from the latter. All the polymers were characterized by gel permeation chromatography, differential scanning calorimetry, and Fourier transform IR spectroscopy. The conductivity data were obtained from alternating current impedance experiments. The results revealed that the copolymer containing both PEG and PTMG as the soft segments showed better performance than TPU containing either PEG or PTMG. The copolymer TPU(PEG/PTMG) proved to be a good gelled electrolyte from 5 to 85°C. This copolymer, impregnated with 150% LiClO₄/PC, possessed good mechanical strength and conductivity as high as 10^?3 S/cm. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 935–942, 2001     

新颖离子导电型聚氨酯弹性体

以低聚二氧戊环磺酸盐(SPDXL)为离子源和增塑剂,聚己二酸乙二醇酯聚氨酯弹性体(EGPU)为基质,设计了一种新颖的正离子导电型聚氨酯弹性体,并对其结构、形态及性能进行了研究。结果表明,通过选取适当平均相对分子质量的磺化低聚醚以及通过控制磺化低聚醚的质量分数,可以优化聚氨酯固体电解质体系的离子导电性能。对于EGPU/SPDXL固体电解质体系,采用SPDXL800的样品具有较高的离子导电性能,其室温离子电导率均达到10-6S/cm以上。     

Ionic and electronic transport in stabilized β-La2Mo2O9 electrolytes

Increasing temperature from 973 to 1173 K leads to a substantial increase of the electronic contribution to the total conductivity of undoped lanthanum molybdate and La₂Mo₂O₉-based solid electrolytes, including La₂Mo_1.7W_0.3O₉, La₂Mo_1.95V_0.05O₉ and La_1.7Bi_0.3Mo₂O₉, where the stabilization of β-La₂Mo₂O₉ down to room temperature was confirmed by high-resolution X-ray diffraction (XRD) and differential scanning calorimetry (DSC) data. In air, the ion transference numbers determined by the modified Faradaic efficiency (FE) technique, decrease from 0.991-0.997 at 973-1023 K down to 0.977-0.984 at 1173 K. Reducing oxygen partial pressure also increases electronic conduction evaluated by the emf and oxygen permeability (OP) measurements, which indicates that the electronic transport is n-type, resulting from decreasing oxygen content in the molybdate lattice. The level of n-type electronic conductivity in air is quite similar for all La₂Mo₂O₉-based ceramics. The results show that these materials can be used as solid electrolytes only under oxidizing conditions and only at temperatures below 1073 K. Their practical applications may also be complicated due to relatively high thermal expansion coefficients (CTEs), (14.1-14.8)×10⁻⁶ K⁻¹ at 300-700 K and (16.4-22.5)×10⁻⁶ K⁻¹ at 850-1070 K, which are close to those of stabilized δ-Bi₂O₃ and γ-Bi₂VO_5.5 electrolytes.     

A study on polyurethane/acrylate crosslinked gel polymer electrolytes

2,4‐Toluene diisocyanate, poly(propylene glycol), poly(ethylene glycol) (PEG) and 2‐hydroxyethyl methacrylate were used to synthesize PEG–UA (urethane acrylate) monomer. The crosslinked polymer and gel polymer electrolytes were prepared in dioxane by free radical polymerization. The swelling behaviour, thermal degradation properties, morphology and ionic conductivity of the gel polymer electrolytes were investigated. With decrease in the proportion of dioxane used, the synthesized polymer's network density increased, its affinity with a solution of 1 M LiClO₄ in propylene carbonate (PC) decreased, and more microgel which diffused in the network. At the same time, the conductivity increased and reached 4 × 10^?4 S cm^?1 at 25 °C. Copyright © 2003 Society of Chemical Industry     

溶胶-凝胶法制备NASICON型Li_(1.15)Y_(0.15)Zr_(1.85)(PO_4)_3固态电解质

以碳酸锂、硝酸锆、磷酸氢二铵和硝酸钇为原料,柠檬酸为络合剂,采用溶胶–凝胶法制备了NASICON型Li1.15Y0.15Zr1.85(PO4)3固态电解质材料,通过无压烧结和放电等离子烧结(SPS)得到固态电解质片。结果表明:采用无压烧结在1 150℃制备的电解质密度可以达到理论密度的95.2%,在室温下晶粒电导率和总电导率分别为2.19×10–4 S/cm和0.86×10–4 S/cm;采用SPS在1 150℃烧结得到的电解质片密度可达到理论密度的96.8%,在室温下样品总电导为0.97×10–4S/cm,激活能为0.44 e V。四方相Zr O2的存在是样品激活能升高的主要原因。     

Synthesis and properties of polyoxyethylated amine polyurethane ionomers

Based on polyoxyethylated amines (M_n = 600, 1,200) derived from n-butyl amine and ethylene oxide, 4,4′-diphenylmethane diisocyanate, and different chain extenders, two series of polyether–polyurethane (PU) ionomers with reasonable mechanical properties were synthesized. Chain-extended by 1,4-butanediol and subsequently reacted with 1,3-propane sultone, PU elastomers can be conveniently converted to PU zwitterionomers whose ions are located in polyether soft segments. Chain-extended by N-methyl diethanolamine or sodium-S-1,2-dihydroxypropyl sulfonate along with ionization by 1,3-propane sultone, PU ionomers with ions incorporated into both hard and soft domains can be prepared. Physical properties were studied by means of Fourier transform infrared spectra, differential scanning calorimetry, and uniaxial stress–strain testing. Complex impedance spectra were also measured to estimate solid-state ionic conductivity. The results show that ionization of both hard and soft segments induced a much decreased glass transition temperature and brought higher ionic conductivity at room temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2179–2185, 1998     

High frequency impedance measurements of sodium solid electrolytes

Solid-state sodium batteries are currently gaining enormous interest as a lower-cost and more environmentally friendly alternative to lithium batteries. They contain significantly less critical rare elements in both the electrolyte and the active material. However, to date, there is no efficient material combination of metallic anode, cathode, and solid electrolyte for room temperature applications that does not require an additional liquid electrolyte while maintaining high energy density. NaPSiO-based glass-ceramics show high ionic conductivity at room temperature, good corrosion resistance against ambient humidity and CO₂, and stability against metallic sodium. However, the conductivity mechanisms of this promising class of materials are currently poorly understood. Herein, high frequency impedance measurements up to 10⁸ Hz shed light on the contributions of grains and grain boundaries to the total impedance, including the distribution of relaxation time constants of the fully crystallized material. In addition, analysis of the temperature dependence allows separation of electrode contributions and determination of activation energies for grain and grain boundary conductivities. Our study provides the basis for fine-tuning the stoichiometry of NaPSiO-based glass-ceramics in terms of maximizing the conductive phase fraction to optimize the performance of future solid-state sodium batteries.     

Study of polyurethane/sulfonated dimethyl fumarate complex

In this study linear polyether polyurethanes (PU) and sulfonated dimethyl fumarate (SDMF) were successfully synthesized and a series of novel solid polymer electrolytes, based on the complexes of PU and SDMF, were prepared. Fourier transform–Raman spectroscopy (FT‐Raman), ¹H‐NMR, differential scanning calorimetry (DSC), atomic force microscopy (AFM), and complex impedance analysis were utilized to investigate the chemical structure, microscale morphology, and ionic conductive property of this system. Results show that the ionic conductivity of the PU/SDMF series increases with increasing temperature. In the salt concentration range investigated, there is a maximum ionic conductivity for the PU/SDMF system. When the molar ratio of the ether oxygen and sodium cation is about 24, the optimum compatibility between the hard and soft segments is realized and the highest soft‐segment T_g is reached. A further increase in salt concentration causes the aggregation and precipitation of SDMF, and the decrease of the soft‐segment T_g. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 67–74, 2002; DOI 10.1002/app.10205     

Conductivity enhancement within garnet-rich polymer composite electrolytes via the addition of succinonitrile

All-solid-state lithium-ion batteries (ASSLIBs) are promising alternatives to conventional organic electrolyte-based batteries due to their higher safety and higher energy densities. Despite advantages, ASSLIBs suffer from issues like high charge transfer resistances due to the brittleness of the inorganic solid electrolyte and chemical instabilities at the lithium/electrolyte interface. Within this work, we investigate composite electrolytes (CEs) based on garnet-type Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO), polyethylene oxide, and lithium bis(trifluoromethanesulfonyl)imide, prepared via a solvent-free cryo-milling approach in contrast to conventional solvent-mediated synthesis. Compositions ranging from polymer-rich to garnet-rich systems are investigated via X-ray diffraction, Raman spectroscopy, and Fourier transform infrared spectroscopy in order to determine the compatibility of the cryo-milling process toward membrane fabrication along with the possible chemical interactions between the composite membrane components. Electrochemical impedance spectroscopy is used to study the role of ceramic to polymer weight fraction on ionic conductivity. It is shown that the addition of succinonitrile (SCN) to the garnet-rich CEs can significantly improve the ionic conductivity compared to the SCN-free CEs.     

Microporous polyurethane/acrylate gel polymer electrolyte obtained by emulsion polymerization

A novel polyurethane/acrylate (PUA) porous gel electrolyte was prepared by a new method, emulsion polymerization. Compared with the traditional phase inversion method, the new method can eliminate the pollution from solvent and decrease the cost of production. The swelling properties and morphology of the porous polymer membranes were characterized. The porous membranes, made by emulsion polymerization, could absorb large quantities of electrolyte solution to form porous gel electrolytes. The gel electrolytes have good solvent retention ability and high ionic conductivity. Copyright © 2004 Society of Chemical Industry     

Li3PO4助熔剂添加对Li1.3Al0.3Ti1.7(PO4)3性质的影响研究

采用溶胶-凝胶法合成Li1.3Al0.3Ti1.7(PO4)3粉末,向Li1.3Al0.3Ti1.7(PO4)3粉末中添加不同摩尔分数的Li3PO4助熔剂烧结制备锂离子固体电解质Li1.3Al0.3Ti1.7(PO4)3烧结片。通过X射线衍射仪、扫描电子显微镜研究合成产物的结构与形貌,采用循环伏安及交流阻抗技术研究合成产物的氧化-还原电位、离子电导率和活化能。结果表明,添加与未添加Li3PO4助熔剂的Li1.3Al0.3Ti1.7(PO4)3烧结片具有相似的X射线衍射结果。添加Li3PO4的Li1.3Al0.3Ti1.7(PO4)3烧结片空隙率较小,更为致密。添加Li3PO4对Li1.3Al0.3Ti1.7(PO4)3的氧化-还原电位影响不大。在所有添加Li3PO4助熔剂的Li1.3Al0.3Ti1.7(PO4)3烧结片中,添加摩尔分数1%Li3PO4的烧结片具有最高的离子电导率6.15×10-4S.cm-1和最低的活化能0.314 2 eV。     

Synthesis and characterization of electrolyte substrate materials based on hyperbranched polyurethane elastomers for anodic bonding

A series of hyperbranched polyurethane elastomers (PEO-HBPUEs) as polymer electrolyte substrate materials was developed for anodic bonding with aluminum (Al) foil in micro-electro-mechanical system (MEMS) devices. The PEO-HBPUEs were prepared by pre-polymerization method with toluene-2,4-diisocyanate(TDI), polypropylene glycol (PPG), 1,4-butanediol(BDO), trimethylolpropane(TMP), lithium bis(trifluoromethanesulphonyl)imide (LiTFSI), and polyethylene oxide (PEO)-based electrolyte in varying proportions via solution casting technique at room temperature. All prepared PEO-HBPUEs exhibited low glass transition temperatures, good thermal stabilities, and suitable mechanical properties. The XRD results showed that PEO-HBPUEs are amorphous, and LiTFSI was well dissolved in the polymer matrix. The component of PEO-based electrolyte in PEO-HBPUEs contributed to increase the ionic conductivity, of which the highest value reached 1.23 × 10⁻³ S/cm at 75°C for PEO-HBPUE4. The anodic bonding of PEO-HBPUE substrate with Al foil was conducted by the coupling action of electric field, temperature field, and pressure field. A clear intermediate bonding layer between the substrate and Al foil was observed and the elements diffusion around bonding layer can be detected by SEM, indicating PEO-HBPUEs and Al foil have been jointed together successfully. The highest tensile strength of the bonding interface of PEO-HBPUE4/Al reached 1.88 MPa. All results demonstrated that the prepared PEO-HBPUEs materials would be promising substrates for flexible MEMS device that can be applied to flexible packaging by anodic bonding technology.     

聚醚聚氨酯/NaClO4/硬段模型化合物的离子导电性能

利用溶液聚合的方法合成了聚醚聚氨酯（PEG－PU）和硬段模型化合物（HD），并以此二者和高氯酸钠为组分，制备了新型聚合物固体电解质。运用傅里叶变换红外吸收光谱、拉曼吸收光谱和交流复阻抗谱对该体系中聚合物－离子之间相互作用和离子导电性能进行了研究。结果表明：PEG－POU－5HD／NaClO4体系聚氨酯中羰基和醚氧基与钠离子之间存在络合竞争；体系的电导率随着温度的上升而提高，且在25－100℃导电行为符合Arrhenius公式；由于硬段模型化合物的加入导致体系离子电导率与盐浓度之间的关系较为复杂。     

PVDF-HFP型凝胶聚合物固体电解质的结构与离子导电性能

以PVDF-HFP为基体聚合物，制备了一系列凝胶聚合物固体电解质膜，其中有机极性介质为碳酸丙烯酯(PC)，电解质盐为LiClO4。通过红外光谱分析、差示扫描量热分析、复阻抗分析等手段对凝胶聚合物固体电解质的结构与离子导电性能进行了研究。结果表明，PC与阳离子之间存在较强的络合作用，PC对基体聚合物有很强的增塑作用。锂盐和PC含量对材料的离子导电性能有较大的影响。随着锂盐和PC含量的增加，材料的离子电导率呈上升趋势。     

Effect of hard segment and concentration of NaClO4 on poly(ethylene oxide)–urethane/NaClO4 complex

Solid poly(ethylene oxide)–urethane electrolytes were prepared from blends of polyurethane and NaClO₄. The samples were characterized by FTIR, DSC, atomic force microscopy, and complex impedance analysis. The effect of the concentration of NaClO₄ on the poly(ethylene oxide)–urethane/NaClO₄ complex were studied. The results showed that the concentration of NaClO₄ had an important effect on the ion–polymer interaction, ion–ion interaction, glass‐transition temperature, morphologic structure, and ionic conductivity of the complex. We also prepared a model compound of hard segments and found that the conductivity of the complex decreased when the model compound was blended into the complex. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2502–2510, 2001