Ionic conductivity of a novel solid polymer electrolyte

A novel kind of solid polymer electrolyte, the solvation unit of which is O?CNHR, has been studied. The effects of host polymer structure, ion species, salt concentration, and plasticizers on ionic conductivity are discussed in detail. The solvability of host polymers is a very important factor that affects the ionic conductivity of electrolytes and is fully decided by the structure of solvation units and their density in polymer chain. The latter two rest with monomers structure and copolymerization ratio. Effects of alkali metal salts and divalent metal salts on ionic conductivity are different because of their different leading factor of cation radius. Salt concentration dependence of ionic conductivity appears as a double‐peak shape when alkali metal salts are added because of the total contribution of two kinds of ionic conductance modes, and appears as similar shapes when divalent metal salts are added. Different influences of plasticizers on ionic conductivity result from their different action ways. Ethylene glycol acts well because of its effective action from three different modes. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2176–2184, 2001     

New polymer bipolar plates for polymer electrolyte membrane fuel cells: Synthesis and characterization

Carbon black (CB) and polyvinylidene fluoride (PVDF) composites were obtained and subsequently characterized, both microstructurally (DSC and DMA) and electrically. In addition, the electrochemical performance of these materials was tested in the form of bipolar plates, expressly manufactured for this purpose and incorporated in a conventional fuel cell. The results obtained allow for the conclusion that CB incorporation into PVDF yields polymer composite materials with electrical conductivity of about 2.4 S/cm, which may be thermically processed and given any convenient shape with the means conventionally applied in the field of polymer technologies. It was found that CB concentration slightly affects the microstructural parameters of the composites (melting temperature, glass‐transition temperature, Avrami kinetic parameters, etc.). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2817–2822, 2002; DOI 10.1002/app.10257     

阻燃聚氨酯基固态聚合物电解质的制备与表征

以聚己二酸-1,4-丁二醇酯二醇(PBA)、六亚甲基二异氰酸酯(HDI)和N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯(FCR-6)为主要原料合成阻燃聚氨酯(TPUP),将阻燃聚氨酯与双(三氟甲烷)磺酰亚胺锂(LiTFSI)复合得到一系列锂盐质量分数不同的阻燃聚氨酯基固态聚合物电解质(TPUP10%Li、TPUP20%Li、TPUP25%Li、TPUP30%Li)。采用红外光谱、热重分析、锥形量热、力学测试、电化学窗口、电导率和电池的充放电性能测试等对阻燃聚氨酯基固态聚合物电解质进行了表征和性能测试。结果表明,TPUP具有良好的阻燃性能,制备的阻燃电解质TPUP25%Li综合性能最佳,且拉伸强度达到2.09MPa,80℃时离子电导率为3.09×10–4S/cm,以TPUP25%Li阻燃聚氨酯基固态聚合物电解质组装的全固态锂电池,在80℃时0.2C电流密度下放电容量达到159 mA·h/g。     

Synthesis and characterization of CdS nanocrystals embedded on solid electrolyte films

In this article nano‐sized CdS crystal embedded in a PEO matrix was successfully prepared by a complex transformation method that is universal for preparing nanosized compounds containing transition metals. The size of embedded CdS particles was in the nanoscale from 2 to 10 nm determined by X‐ray diffusion. The nanosized CdS displayed the expected blue shift of the onset absorbance in the UV spectrum. The amount of blue shift depends upon the dipping time of the PEO–cadmium complex film in a sodium sulfide solution as well as its concentration. The most effective means for adjusting the size of CdS nanocrystals is to change the ratio of the oxygen along with the PEO chain to the cadmium ion in the complex film. The alkali salt in the film would contribute to the conductivity of the composite film. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1263–1268, 2002; DOI 10.1002/app.10459     

全固态聚合物电解质的性能研究

聚合物电解质由于本身的优点,已成为锂离子电池研究的一个热点.聚合物电解质由聚合物、锂盐及添加剂组成,本文综述了聚合物电解质研究的新体系,论述了聚合物电解质中各组分对其性能的影响.     

Electro-organic synthesis without supporting electrolyte: Possibilities of solid polymer electrolyte technology

The application of ion exchange membranes as solid polymer electrolytes (SPE) in fuel cells is state-of-the-art. This technology needs no supporting electrolyte; consequently it can be applied for electro-organic syntheses in order to save process steps. In this case the process is not predetermined to a maximized energy efficiency so that the selection of the cell design, of the electrode materials and of the operating conditions can be focused on a high selectivity of the electrode reactions. The electro-osmotic stream, which is caused by the solvation shells of the ions during their migration through the membrane, and hence is a typical property of SPE technology, has a significant effect on the electrode reactions. It generates enhanced mass transfer at the electrodes, which is beneficial for reaction selectivity. It can be influenced by the choice of, and possibly by the preparation of, the membrane. An additional remarkable advantage of SPE technology is the exceptional long durability of oxide coated electrodes. By combination of several process engineering methods stable operation of SPE cells has been realized, even for examples of non-aqueous reaction systems. Experiments up to 6000 h duration and in cells of up to 250 cm² membrane area show the potential for industrial application.     

Synthesis and characterization of Nafion-stabilized Pt nanoparticles for polymer electrolyte fuel cells

Platinum nanoparticles are synthesized by alcohol reduction method using Nafion as a stabilizer under various conditions such as the Nafion/Pt molar ratio and reflux temperature. Nafion-Pt nanoparticles are characterized by agglomeration and the particle size is typically in the range of 2-4 nm. The electrocatalytic activity of Nafion-Pt nanoparticles for polymer electrolyte and direct methanol fuel cells (PEFCs and DMFCs) is investigated in comparison to that of unsupported Pt black and carbon-supported Pt/C electrocatalysts. Nafion-Pt nanoparticles prepared with low Nafion/Pt ratios show higher and/or comparable activities towards O₂ reduction reaction in the absence and presence of methanol in comparison to that of Pt black and Pt/C electrocatalysts. In contrast, the electrocatalytic activity of the Nafion-Pt nanoparticles for the methanol oxidation reaction is very low. The results indicate that Pt nanoparticles embedded in Nafion polyelectrolyte are potential methanol tolerant electrocatalysts for the O₂ reduction reaction in DMFCs.     

Preparation and properties of a novel green solid polymer electrolyte for all-solid-state lithium battery

Solid polymer electrolyte (SPE)-based lithium batteries have easy processing and safety for energy vehicles and storage. However, the preparation process of SPEs mostly used a lot of organic solvents, which will threaten human living space and body health. Herein, a novel green solid polymer electrolyte (ionic liquid type waterborne polyurethane, IWPUS) without no organic solvents was prepared from hybrids of ionic liquid-based waterborne polyurethane (IWPU) and LiClO₄. The structure and properties of IWPUS were investigated by IR, SEM, XRD, TGA, ion conductivity test. The results showed that Li⁺ of LiClO₄ could coordinate with  CO and  C O C in the polyurethane matrix. LiClO₄ had been well dispersed in IWPU. The conductivity of IWPUS increased with the increase of LiClO₄ content. The higher conductivity of IWPUS with 20% LiClO₄ at 80°C was 1.8 × 10⁻⁴ s•cm⁻¹. IWPUS based on ionic liquid-based waterborne polyurethane would be promised to become an environmentally friendly candidate for all solid-state lithium ion batteries.     

Synthesis and characterization of a new hyperbranched organic–inorganic solid polymer electrolyte with cyanuric chloride as a core element

A new hyperbranched organic–inorganic hybrid electrolyte based on the use of 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride, CC) as the coupling core to couple with oligo(oxyalkylene)-amines, followed by condensation with (3-glycidoxypropyl)-trimethoxysilane (GLYMO) and complexed with LiClO₄, has been prepared and characterized. The Vogel–Tamman–Fulcher (VTF) like conductivity behavior is observed in the present organic–inorganic hybrid electrolytes with a maximum ionic conductivity value of 4.4 × 10⁻⁵ S cm⁻¹ at 30 °C. Multinuclear NMR techniques are used to provide a microscopic view for the specific interaction between the polymer chains and Li⁺ cations and their dynamic behaviors. The results of 2D ¹H–¹³C wide-line separation (WISE) and ⁷Li static line NMR width measurements divulge that the mobility of the ⁷Li cations is strongly related to a dynamic environment created by the polymer motion in the amorphous phase. The combined results of conductivity and ⁷Li pulse-gradient spin-echo (PGSE) NMR self-diffusion coefficient measurements reveal that the conductivity enhancement at low salt concentrations is mainly caused by the high mobility of the lithium cations.     

阻燃聚氨酯基固态聚合物电解的制备

摘要：以聚己二酸-1,4-丁二醇酯二醇( PBA) 、六亚甲基二异氰酸酯( HDI)和阻燃剂N，N阻双（2（羟乙基）胺基亚甲基磷酸二乙酯( FCR-6）为主要原料合成阻燃聚氨酯（TPUP），将阻燃聚氨酯与锂盐复合得到阻燃聚氨酯基固态聚合物电解质。采用红外光谱、热重分析、锥形量热、力学测试、电化学窗口、电导率和电池的充放电性能测试等对阻燃聚氨酯基固态聚合物电解质进行了表征和性能测试。研究表明，TPUP具有良好阻燃性能，制备的阻燃电解质TPUP25%Li综合性能最佳，且拉伸强度达到2.09MPa，80℃时离子电导率为3.09M10-4 S/cm，以阻燃电解质组装的全固态锂电池，在80℃时0.2C电流密度下放电容量达到159mA?h/g。     

Synthesis and characterization of novel crosslinked polyurethane–acrylate electrolyte

Flexible, transparent, and crosslinked polymer films were synthesized by polymerization of PEG‐modified urethane acrylate using a simple method. A series of novel solid polymer electrolytes and gel electrolytes were prepared based on this type of polymer film. To understand the interactions among salt, solvent, and polymer, the swelling behaviors of the crosslinked polymer in pure propylene carbonate (PC) and liquid electrolyte solutions (LiClO₄/PC) were investigated. The results showed that the swelling rate in the electrolyte solution containing moderate LiClO₄ was greater than that in pure PC. Thermogravimetric analysis (TGA) also supported the interaction between the solvent and polymer. The morphology and crystallinity of the crosslinked polymer and polymer electrolytes were studied using atomic force microscopy (AFM) and wide‐angle X‐ray diffraction (WAXD) spectroscopy. The effects of the content of the electrolyte solution on the ionic conductivity of gel electrolytes were explored. The dependence of the conductivity on the amount of the electrolyte solution was nonlinear. With a different content of the plasticizer, the ionic conduction pathway of the polymer electrolytes would be changed. The best ionic conductivity of the gel electrolytes, which should have good mechanical properties, was 4 × 10^r?3 S cm^?1 at 25°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 340–348, 2003     

A unitized approach to regenerative solid polymer electrolyte fuel cells

In this work on regenerative fuel cells, the initial part deals with water electrolysis using a cell design that closely resembled that of a solid polymer fuel cell. The electrolytes were Nafion® 117 and the Dow experimental membrane. The electrodes were Pt-on-C and Pt/Ir-on-C gas diffusion electrodes on the oxygen side and Pt-on-C on the hydrogen side. Fuel cells were built with the above mentioned electrodes and membranes. These cells were run to obtain fuel cell and electrolysis data. Data for a maximum of five regenerative cycles were obtained. The current-potential data in the regenerative electrolysis were characterized by a gradual decay with time. The fuel cell data were very stable. The membrane-electrode assemblies were found in very good condition, and no visible corrosion of electrodes was evident.     

蚕丝/聚氧化乙烯复合固态聚合物电解质

以天然蚕丝为骨架支撑材料,将聚氧化乙烯(PEO)和锂盐溶液浇铸在蚕丝上干燥成膜,制备得到蚕丝/PEO复合固态聚合物电解质(Silk-PEO-SPE)。通过FTIR、电子拉力机、同步热分析仪、电化学窗口测试、电导率测试对固态聚合物电解质进行了结构和性能表征,并以磷酸铁锂为正极,金属锂为负极组装全固态电池,测试了电池的充放电性能。结果表明,与传统PEO固态聚合物电解质相比,复合固态聚合物具有较好的机械强度(达到10 MPa)和优异的电化学窗口(达到4.6 V),以该电解质组装的全固态锂电池在60℃、1 C电流密度下放电比容量达到113 mA·h/g,循环100次容量保持率达到97%,显示出较优异的循环稳定性。     

侧挂聚醚和烷基磺酸锂的单离子梳状聚合物电解质的合成与性能

采用α 烯丙基聚醚(UPEO)/烯丙基磺酸锂(LS)/苯乙烯(St)共聚反应,合成得到一种以聚烯烃链为主链、侧挂聚醚和烷基磺酸锂的新型单离子梳状聚合物电解质(CPPL)。通过元素分析、IR、GPC以及DSC等对其结构与形态进行了分析表征。研究了反应物料配比、催化剂、反应时间等因素对CPPL物理性能的影响。研究结果表明:该类聚合物电解质膜材料的θg值和成膜性能主要取决于单体原料配比,CPPL室温电导率可达9.3×10-3s/cm。     

一种新型共轭Schiff碱聚合物的合成与表征

以对苯二甲醛和水合肼为原料,无水乙醇作溶剂合成了一种共轭Schiff碱聚合物,并通过GPC、IR、1 H NMR、紫外-可见吸收光谱和荧光光谱对其分子量和组成结构进行表征。结果表明,该物质为一种分子量较大的共轭Schiff碱聚合物,具有良好的荧光性。     

新型两性高分子污泥脱水剂PADS的合成及其表征

以丙烯酰胺(AM)、丙烯酰氧乙基三甲基氯化铵(DAC)和甲基丙烯磺酸钠(SMAS)为单体,采用三元自由基水溶液共聚法合成两性污泥脱水剂P(AM-DAC-SMAS),简称为PADS。利用响应面法考察了三元单体配比、引发剂含量、反应温度、反应时间、pH等对PADS合成的影响。结果表明,最佳合成条件为:单体配比n(AM)∶n(DAC+SMAS)=4.00∶1,引发剂质量分数为0.1%,反应时间3 h,反应温度40℃,体系pH值为6.5,搅拌速度为150 r/min。当PADS的投加量为7 mg/g干泥时,污泥达到最佳脱水效果,污泥含水率W_c可由98.56%降为75.05%,污泥比阻SRF由2.98×10⁽¹³⁾m/kg降为1.23×10(13)m/kg降为1.23×10⁽¹³⁾m/kg。     

新型两性高分子污泥脱水剂PADS的合成及其表征

以丙烯酰胺(AM)、丙烯酰氧乙基三甲基氯化铵(DAC)和甲基丙烯磺酸钠(SMAS)为单体,采用三元自由基水溶液共聚法合成两性污泥脱水剂P(AM-DAC-SMAS),简称为PADS。利用响应面法考察了三元单体配比、引发剂含量、反应温度、反应时间、pH等对PADS合成的影响。结果表明,最佳合成条件为:单体配比n(AM)∶n(DAC+SMAS)=4.00∶1,引发剂质量分数为0.1%,反应时间3 h,反应温度40℃,体系pH值为6.5,搅拌速度为150 r/min。当PADS的投加量为7 mg/g干泥时,污泥达到最佳脱水效果,污泥含水率W_c可由98.56%降为75.05%,污泥比阻SRF由2.98×10~(13)m/kg降为1.23×10~(13)m/kg。     

Synthesis and characterization of a novel highly phosphonated water-insoluble polymer

A novel polymer, functionalized by tetrafluoroaryl phosphonic acid units, was prepared by free-radical polymerization of the corresponding styrene monomer. The obtained polymer was analyzed by gel permeation chromatography, differential scanning calorimetry, and spectroscopy (NMR, IR). Ion exchange capacity of the water-insoluble polymer was determined in methanol solution by titration with 0.1M NaOH. The proton conductivity of the polymer of 9.91 × 10⁻⁷ S cm⁻¹ as disclosed by electrochemical impedance spectroscopy renders this polymer a promising candidate for solid electrolyte applications or as a water-insoluble dopant for proton exchange membrane applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48235.     

固体聚合物电解质膜臭氧生成技术

本文对固体聚合物电解质膜生成臭氧技术进行了介绍。该技术具有装置小型化、臭氧浓度高、电流效率大等特点。由于该技术的核心部件三合一膜电极(MEA)成本较高,电催化剂效率低,本文介绍了一些改进膜电极结构的措施以提高电极性能。