Stabilized heteropolyacid/Nafion composite membranes for elevated temperature/low relative humidity PEFC operation

Organic/inorganic composite membranes with different inorganic heteropolyacid (HPA) additives maintain sufficient proton conductivities for atmospheric pressure elevated temperature (>100 °C) polymer electrolyte fuel cell (PEFC) operation. However, membrane and membrane electrode assembly (MEA) processing is severely curtailed because of the solubility of the HPA additives in aqueous media. Composite membranes with the HPA (phosphotungstic acid; PTA) additive rendered insoluble by ion exchanging protons with larger cations such as Cs⁺, NH₄⁺, Rb⁺ and Tl⁺ were fabricated. The additive loss in aqueous media was lowered from nearly 100% (unmodified HPA) to about 5% (modified HPA). The membranes were robust, and demonstrated low H₂ crossover currents of around 2 mA/cm² for a 28 μm thick membrane. All membranes were evaluated at high temperatures and low relative humidities in an operating fuel cell. The conductivities of the composite membranes at 120 °C and 35% relative humidity were on the order of 1.6 × 10⁻² S/cm.     

Fabrication and characterization of PFSI/ePTFE composite proton exchange membranes of polymer electrolyte fuel cells

PFSI/ePTFE composite proton exchange membranes were fabricated by impregnating perfluorosulfonic acid resin (PFSI resin, Nafion) into chemically modified expanded PTFE (ePTFE) matrix. Chemical modification of sodium-naphthalene treatment and N-methylol acrylamide (NMA) grafting decreased the contact angle of the as-received ePTFE from 125 ± 0.5° to 67 ± 0.5°, effectively converting the as-received hydrophobic ePTFE to a hydrophilic ePTFE matrix. The composite membrane fabricated with the hydrophilic ePTFE have higher impregnated PFSI loading, much lower porosity and better PTFE/PFSI interface contact, as compared to the composite membranes with the as-received ePTFE. This leads to much lower gas permeability and significantly improves the durability under an accelerated dry/wet cycle test. The fuel cell made from the PFSI/ePTFE composite membranes with hydrophilic ePTFE showed superior performance as compared to that with the composite membrane made from the as-received ePTFE and Nafion 211 membrane.     

Polymer gel electrolytes prepared from P(EG‐co‐PG) and their nanocomposites using organically modified montmorillonite

Polymer gel electrolytes were prepared by thermal crosslinking reaction of a series of acrylic end‐capped poly(ethylene glycol) and poly(propylene glycol) [P(EG‐co‐PG)] having various geometries and molecular weights. Acrylic end‐capped prepolymers were prepared by the esterification of low molecular weight (M_n: 1900–5000) P(EG‐co‐PG) with acrylic acid. The linear increase in the ionic conductivity of polymer gel electrolyte films was observed with increasing temperature. The increase in the conductivity was also monitored by increasing the molecular weight of precursor polymer. Nanocomposite electrolytes were prepared by the addition of 5 wt % of organically modified layered silicate (montmorillonite) into the gel polymer electrolytes. The enhancement of the ionic conductivity as well as mechanical properties was observed in the nanocomposite systems. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 894–899, 2004     

用于测定钢液低氧含量的双层固体电解质研究

采用“毛坯浆料法”在ＺｒＯ２（９％摩尔含量ＭｇＯ）管状固体电解质基体表面制备了厚度为１－４μｍ的ＺｒＯ２（１０％摩尔含量Ｙ２Ｏ３）固体电解质涂层，并分别对此在本实验室和美国ＬｅｅｄｓａｎｄＮｏｒｔｈｒｕｐ公司进行了钢液低氧含量测试，结果表明：涂层没有破坏基体的抗热震性：氧浓差电池电动势的重现性偏差由原来的±２ｍＶ；电动势的绝对值提高１０ｍＶ左右；而比日本Ｔｏｒａｙ公司的同类产品提高３５ｍＶ，这说明     

Characterization of poly(vinylidenefluoride-co-hexafluoropropylene)-based polymer electrolyte filled with TiO2 nanoparticles

Nanoscale TiO₂ particle filled poly(vinylidenefluoride-co-hexafluoropropylene) film is characterized by investigating some properties such as surface morphology, thermal and crystalline properties, swelling behavior after absorbing electrolyte solution, chemical and electrochemical stabilities, ionic conductivity, and compatibility with lithium electrode. Decent self-supporting polymer electrolyte film can be obtained at the range of <50 wt% TiO₂. Different optimal TiO₂ contents showing maximum liquid uptake may exist by adopting other electrolyte solution. Room temperature ionic conductivity of the polymer electrolyte placed surely on the region of >10⁻³ S/cm, and thus the film is very applicable to rechargeable lithium batteries. An emphasis is also be paid on that much lower interfacial resistance between the polymer electrolyte and lithium metal electrode can be obtained by the solid-solvent role of nanoscale TiO₂ filler.     

基于支持向量回归的动力电池参数辨识

根据铅酸蓄电池在放电过程中内部电化学反应导致外部电特性变化的特点,提出一种基于支持向量机原理的电解液密度辨识模型。利用支持向量机理论非线性回归的特性,简化测量电解液密度的过程,在恶劣环境下检测动力电池的电解液密度更显其优越性。预测实验表明,采用改进的交叉验证预测模型具有泛化能力强、稳定性好的特点,并且在小样本的条件下能达到预期的辨识精度。     

一种能够抑制锂枝晶的锂金属电池电解液润湿性添加剂

将氟代有机溶剂2,2,3,3-四氟丙基甲基丙烯酸酯(TFPMA)作为双功能添加剂引入碳酸酯电解液体系,考察了TFPMA质量分数对增大润湿性的影响.采用交流阻抗、恒流充放电等测试了添加TFPMA后的锂金属电池性能.采用SEM和XPS表征了循环后的锂金属电极表面.结果表明,1.0％(质量分数,下同)TFPMA的添加使电解液与隔膜间的接触角从54°降至44°,内阻从6.15Ω降至1.94Ω,Li-LiFePO4电池在5 C电流密度下的比容量从66 mA·h/g提升至80 mA·h/g,1 C电流密度下的恒电流循环在100圈时还保持99％以上的库仑效率.TFPMA还促进了Li+的均匀沉积和优良固体电解质界面膜的形成,抑制了锂枝晶,电解液添加了1.0％TFPMA后,Li-Cu电池可以循环100圈以上,而库仑效率没有发生较大下降.循环后电极的SEM图表明,添加了1.0％TFPMA电解液的锂金属负极表面沉积更加平整,有较少的锂枝晶生成.     

Comparative study on the preparation and properties of radiation‐grafted polymer electrolyte membranes based on fluoropolymer films

In this study the fluoropolymers, poly(ethylene‐co‐tetrafluoroethylene) (ETFE) and poly(vinylidene fluoride) (PVDF) films, together with the radiation‐induced crosslinked polytetrafluoroethylene (cPTFE) film were compared on the basis of their preparation and properties of radiation‐grafted polymer electrolyte membranes. The polymer electrolyte membranes were prepared by radiation grafting of styrene into the base films and subsequent sulfonation. The proton conductivity and chemical stability of the three types of membranes with a similar ion exchange capacity (IEC) near 1.0 mmol/g were investigated and are discussed in detail. Although the ETFE‐based polymer electrolyte membrane was relatively more stable, its proton conductivity was lower than those of the PVDF‐ and cPTFE‐based membranes. On the other hand, the cPTFE‐based membrane showed a significantly higher proton conductivity, but its chemical stability was shorter than that of the ETFE‐based membrane. It is considered that the difference in the preparation and properties of the polymer electrolyte membranes was due to the difference in the degree of crystallinity as well as in the chemical structure of the fluoropolymer base films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1966–1972, 2007     

Lithium/V6O13 cells using silica nanoparticle-based composite electrolyte

The electrochemical behavior of Li/V₆O₁₃ cells is investigated at room temperature (22 °C) both in liquid electrolyte consisting of oligomeric poly(ethyleneglycol)dimethylether+lithium bis(trifluoromethylsulfonylimide) and composite electrolytes formed by blending the liquid electrolyte with silica nanoparticles (fumed silica). The addition of fumed silica yields a gel-like electrolyte that demonstrates the desirable property of suppressing lithium dendrite growth due to the rigidity and immobility of the electrolyte structure. The lithium/electrolyte interfacial resistance for composite gel electrolytes is less than that for the corresponding base-liquid electrolyte, and the charge-discharge cycle performance and electrochemical efficiency for the Li/V₆O₁₃ cell is significantly improved. The effect of fumed silica surface group on the electrochemical performance is discussed; the native hydrophilic silanol surface group appears better than fumed silica that is modified with a hydrophobic octyl surface moiety.     

A study on capacity fading of lithium-ion battery with manganese spinel positive electrode during cycling

The capacity fading mechanism of lithium-ion cell was studied by disassembling the charge-discharged cells and analyzing their electrodes using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), etc. Cu ion dissolved from current collector of anode and Mn ion dissolved from LiMn₂O₄ spinel (cathode) were all existing in solid electrolyte interface (SEI) layer on carbon anode as Cu₂O and MnO or MnO₂, respectively. These depositions of Cu and Mn oxides did not uniformly deposited on the anode side, and most of them were detected on the carbon surface nearby to the separator side. The SEI layer is hard and about 0.3 μm in thickness. Furthermore, the cycling performance of the cells can be improved by adding 1,2,3-benzotrazole (a corrosion inhibitor of Cu) before assembling the cell, it then coordinates strongly with Cu ions into the electrolyte. From the results, it is obvious that the existing of Cu oxide as well as Mn oxide in the SEI layer, which blocks the normal intercalation of the lithium ions, is one of the factors for the capacity fading of the cells.