Halogen acid electrolysis in solid polymer electrolyte cells

The use of solid polymer electrolyte systems has been extended to the electrolysis of aqueous HCl and HBr. The reduced internal losses in these cells permits the production of hydrogen and the halogen at an energy consumption considerably less than that reported previously. Data are presented for the operational characteristics of the solid polymer electrolyte acid electrolysers operating over a range of current densities, pressures, feedstock compositions, and temperatures.     

Electrochemical properties and performance of poly(acrylonitrile)-based polymer electrolyte for Li/LiCoO2 cells

It has been demonstrated that LiCoO₂ is a very attractive cathode active material for lithium rechargeable cells. Poly(acrylonitrile) (PAN)-based polymer electrolyte is used for Li/LiCoO₂ cells. PAN-based polymer electrolyte shows ionic conductivity of the order 1 mS cm⁻¹ at room temperature, irrespective of time evolution, and wide electrochemical stability up to 4.3 V (versus Li⁺/Li). An LiCoO₂ composite cathode containing 4 wt.% conductive material displays a good cycling performance. From a.c. impedance results, the interfacial resistance of Li/LiCoO₂ cells is dominated by the passive layer formed at the lithium/polymer electrolyte interface.     

Heteropolyacid-impregnated PVDF as a solid polymer electrolyte for dye-sensitized solar cells

Heteropolyacid (HPA)-impregnated polyvinylidene fluoride (PVDF) with iodine/iodide was prepared as a new polymer electrolyte for bio-mimicking natural photosynthesis. With this new polymer electrolyte, dye-sensitized solar cell was fabricated using N3 dye-adsorbed over TiO₂ nanoparticles (photoanode) and conducting carbon cement coated on conducting glass (photocathode). The fabricated cell generates high open circuit voltage (V_OC 426 mV) and short circuit current (I_SC 3.90 mA) upon illumination with visible light. It is also demonstrated that the polymer electrolytes prevent the back-electron transfer reactions taking place in dye-sensitized hetero-junctions and are highly promising for solar energy conversion to electricity.     

Gel polymer electrolyte lithium-ion cells with improved low temperature performance

For a number of NASA's future planetary and terrestrial applications, high energy density rechargeable lithium batteries that can operate at very low temperature are desired. In the pursuit of developing Li-ion batteries with improved low temperature performance, we have also focused on assessing the viability of using gel polymer systems, due to their desirable form factor and enhanced safety characteristics. In the present study we have evaluated three classes of promising liquid low-temperature electrolytes that have been impregnated into gel polymer electrolyte carbon-LiMn₂O₄-based Li-ion cells (manufactured by LG Chem. Inc.), consisting of: (a) binary EC + EMC mixtures with very low EC-content (10%), (b) quaternary carbonate mixtures with low EC-content (16–20%), and (c) ternary electrolytes with very low EC-content (10%) and high proportions of ester co-solvents (i.e., 80%). These electrolytes have been compared with a baseline formulation (i.e., 1.0 M LiPF₆ in EC + DEC + DMC (1:1:1%, v/v/v), where EC, ethylene carbonate, DEC, diethyl carbonate, and DMC, dimethyl carbonate). We have performed a number of characterization tests on these cells, including: determining the rate capacity as a function of temperature (with preceding charge at room temperature and also at low temperature), the cycle life performance (both 100% DOD and 30% DOD low earth orbit cycling), the pulse capability, and the impedance characteristics at different temperatures. We have obtained excellent performance at low temperatures with ester-based electrolytes, including the demonstration of >80% of the room temperature capacity at −60 °C using a C/20 discharge rate with cells containing 1.0 M LiPF₆ in EC + EMC + MB (1:1:8%, v/v/v) (MB, methyl butyrate) and 1.0 M LiPF₆ in EC + EMC + EB (1:1:8%, v/v/v) (EB, ethyl butyrate) electrolytes. In addition, cells containing the ester-based electrolytes were observed to support 5C pulses at −40 °C, while still maintaining a voltage >2.5 V at 100 and 80% state-of-charge (SOC).     

Simulation analysis of a system combining solid oxide and polymer electrolyte fuel cells

We evaluated the performance of system combining a solid oxide fuel cell (SOFC) stack and a polymer electrolyte fuel cell (PEFC) stack by a numerical simulation. We assume that tubular-type SOFCs are used in the SOFC stack. The electrical efficiency of the SOFC–PEFC system increases with increasing oxygen utilization rate in the SOFC stack. This is because the amount of exhaust heat of the SOFC stack used to raise the temperature of air supplied to it decreases as its oxygen utilization rate increases and because that used effectively as the reaction heat of the steam reforming reaction of methane in the stack reformer increases. The electrical efficiency of the SOFC–PEFC system at 190 kW ac is 59% (LHV), which is equal to that of the SOFC-gas turbine combined system at 1014 kW ac.     

Fabrication and charge/discharge behaviour of some lithium solid polymer electrolyte cells

A report is given of the fabrication of some laboratory model lithium cells using solid polymer electrolytes (SPE). These SPEs are based on poly(ethylene oxide) (PEO) and lithium picrate/lithium lactate salts. Electrochemical parameters (i.e., open-circuit potential, short-circuit current) and the discharge behaviour under different current drains of these cells are studied. The behaviour of cells with SPE blended with plasticizer like polyethylene glycol is also examined. It has been observed that a lithium cell with a PEO/lithium picrate electrolyte in combination with a picrate-doped polypyrrole cathode behaves excellently compared with other systems. The results are explained in terms of higher ion conductivity of PEO/picrate salt complexes.     

Li3PS4固态电解质的研究进展

全固态锂电池因其高安全性和高能量密度成为最有望替代传统液态锂电池的体系之一.固态电解质是全固态锂电池的核心组成部分,其中硫化物电解质因其高离子电导率、良好的机械延展性等优势成为最具潜力的固态电解质之一.Li3PS4固态电解质具有高离子电导率、宽电化学窗口、低成本等优势,是极具代表的硫化物固态电解质,也是近年来研究较多的...     

Quasi solid state polymer electrolyte with binary iodide salts for photo-electrochemical solar cells

Quasi-solid-state polymer electrolytes can be used in dye sensitized solar cells (DSSCs) in order to overcome various problems associated with liquid electrolytes. Prior to fabricating commercially viable solar cells, the efficiency of quasi solid state DSSCs needs to be improved. Using electrolytes with a binary iodide mixture is a novel technique used to obtain such efficiency enhancement. In this work we report both conductivity and solar cell performance enhancements due to incorporation of a mixture containing LiI and tetrahexylammonium iodide in a quasi-solid-state electrolyte. The conductivity of the electrolyte increases with added amounts of LiI and thus the highest conductivity, 3.15 × 10⁻³ S cm⁻¹ at 25 °C, is obtained for the electrolyte 100 wt% LiI. The predominantly ionic behavior of the electrolytes was established from dc polarization measurements. The iodide ion conductivity, measured using iodine pellet electrodes decreased somewhat with increasing amount of LiI even though the overall conductivity increased. However, the highest efficiency was obtained for the DSSC containing a polymer electrolyte with Hex₄N⁺I^¯:LiI = 1:2 mass ratio. This cell had the largest short circuit current density of about 13 mA cm⁻² and more than 4% overall energy conversion efficiency. The results thus show that electrolytes with Hex₄N⁺I^¯/LiI mixed iodide system show better DSSC performance than single iodide systems.     

Comparative performance and thermoeconomic analyses of high temperature polymer electrolyte membrane based two hybrid systems

The main objective of this study is to compare the two systems in terms of the thermoeconomic and the performance. The first one is called hybrid I and consists of high temperature polymer electrolyte membrane and thermocapacitive cycle. The second one is named hybrid II, which is composed of high temperature polymer electrolyte membrane and thermoelectric generator. Thermocapacitive cycle and thermoelectric generator have various advantages, such as generally lower cost and higher power density. So, they have good potential to utilize waste heat. The performance parameters of the considered hybrid systems include power density, energy efficiency, exergy efficiency and exergy destruction rate. The results have shown that hybrid I is more advantageous than hybrid II. The maximum power density values for hybrid I and hybrid II are obtained to be 2536.91W and 2049.62W while their energy efficiencies are 77.4% and 76.8%, respectively.     

Effects of anode and electrolyte microstructures on performance of solid oxide fuel cells

To improve the performance of anode-supported solid oxide fuel cells (SOFCs), various types of single cells are manufactured using a thin-film electrolyte of Yttria stabilized zirconia (YSZ) and an anode functional layer composed of a NiO–YSZ nano-composite powder. Microstructural/electrochemical analyses are conducted. Single-cell performances are highly dependent on electrolyte thickness, to the degree that the maximum power density increases from 0.74 to 1.12 W cm⁻² according to a decrease in electrolyte thickness from 10.5 to 6.5 μm at 800 °C. The anode functional layer reduced the polarization resistance of a single cell from 1.07 to 0.48 Ω cm² at 800 °C. This is attributed to the provision by the anode layer of a highly reactive and uniform electrode microstructure. It is concluded that optimization of the thickness and homogeneity of component microstructure improves single-cell performances.     

Influence of ionic pretreatment on the performance of solid electrolyte dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs) were manufactured with liquid iodine/iodide electrolyte solution in acetonitrile and a solid electrolyte based on plasticized poly(ethylene oxide) (PEO). Two types of titania electrodes manufactured from two-ingredient precursors were used to assess the efficacy of the solid electrolyte and the improvement produced by two chemical treatments. Solid electrolyte devices with a liquid electrolyte pretreatment applied to the electrolyte-oxide interface demonstrated improved photovoltaic performance compared to untreated solid electrolyte devices and solid electrolyte devices given an electrode-bulking sol treatment. Devices using electrodes made from hydrothermally synthesized titanate nanotubes resulted in lower performance than those made from the typically-used titania nanopowder, with significant performance loss resulting from the substitution of solid for liquid electrolyte, indicating the critical dependence of performance on electrolyte infiltration into the oxide layer.     

Membrane water-flow rate in electrolyzer cells with a solid polymer electrolyte (SPE)

Water-flow rate across Nafion membrane in SPE electrolyzer cells was measured and modelled. From the analysis of water transport mechanisms in SPE water electrolysis, the water-flow rate through membrane can be described by the electro-osmotic drag. The calculated electro-osmotic drag coefficients, n_d, for the membrane in SPE electrolysis cells at different temperatures were compared with literature and in good agreement with those of Ge et al. and Ise et al. To describe the water-flow rate through membrane more accurately, a linear fit of n_d as a function of temperature for the membrane in SPE water electrolysis was proposed in this paper. This paper studied the membrane water-flow rate experimentally and mathematically, which is of importance in the designing and optimization of the process of SPE water electrolysis. This paper also provided a novel method for measuring the electro-osmotic drag coefficient of Nafion membrane in contact with liquid water, acid and methanol solutions, etc.     

Four volts class solid lithium polymer batteries with a composite polymer electrolyte

Polyethylene oxide (PEO)-based polymer electrolytes with BaTiO₃ as a filler have been examined as electrolytes in 4 V class lithium polymer secondary batteries. A mixture of 90 wt.% LiN(CF₃SO₂)₂–10 wt.% LiPF₆ was found to be the best candidate as the salt in PEO, and showed high electrical conductivity, good corrosion resistance to the aluminum current collector and low interfacial resistance between the lithium metal anode and the polymer electrolyte. The cyclic performance of the cell, Li/[PEO₁₀–(LiN(CF₃SO₂)₂–10 wt.% LiPF₆)]–10 wt.% BaTiO₃/LiNi_0.8Co_0.2O₂/Al, showed good charge–discharge cycling performance. The observed capacity fading on charging up to 4.2 V at 80 °C in the cell was about 0.28% per cycle in the first 30 cycles, compared to that of 0.5% for the polymer electrolyte without LiPF₆ in the lithium salt.     

High discharge capacity solid composite polymer electrolyte lithium battery

In this study, a series of nanocomposite polymer electrolytes (CPEs), PAN/LiClO₄/SAP, with high conductivity are prepared based on polyacrylonitrile (PAN), LiClO₄ and low content of the silica aerogel powder (SAP) prepared by the sol-gel method with ionic liquid (IL) as the template. The effect of addition of SAP on the properties of the CPEs is investigated by FTIR, AC impedance, linear sweep voltagrams and cyclic voltammetry measurements as well as the charge-discharge performance. It is found that the ionic conductivity of the CPE is significantly improved by addition of SAP. The maximum ambient ionic conductivity of CPEs is about 12.5 times higher than that without addition of SAP. The results of the voltammetry measurements of CPE-3, which contained 3 wt% of SAP, show that the anodic and cathodic peaks are well maintained after 100 cycles, showing excellent electrochemical stability and cyclability over the potential range between 0 V and 4 V vs. Li/Li⁺. Besides, the room temperature discharge capacity measured at 0.5C for the coin cell based on CPE-3 is 120 mAh g⁻¹ and the capacity is retained after 20 cycles discharge, indicating the potential for practical use. This is perhaps the first report of the room temperature charge-discharge performance on the solid composite polymer electrolyte to the best of our knowledge.     

Toward high performance solid-state lithium-ion battery with a promising PEO/PPC blend solid polymer electrolyte

A promising solid polymer blend electrolyte is prepared by blending of poly(ethylene oxide) (PEO) with different content of amorphous poly(propylene carbonate) (PPC), in which the amorphous property of PPC is utilized to enhance the amorphous/free phase of solid polymer electrolyte, so as to achieve the purpose of modifying PEO-based solid polymer electrolyte. It indicates that the blending of PEO with PPC can effectively reduce the crystallization and increase the ion conductivity and electrochemical stability window of solid polymer electrolyte. When the content of PPC reaches 50%, the ionic conductivity reaches the maximum, which is 2.04 × 10⁻⁵ S cm⁻¹ and 2.82 × 10⁻⁴ S cm⁻¹ at 25°C and 60°C, respectively. The electrochemical stability window increases from 4.25 to 4.9 V and the interfacial stability of lithium metal anode is also greatly improved. The solid-state LiFePO₄//Li battery with the PEO/50%PPC blend solid polymer electrolyte has good cycling stability, which the maximum discharge specific capacity is up to 125 mAh g⁻¹ at a charge/discharge current density of 0.5 C at 60°C.     

Dynamic modeling of the effect of water management on polymer electrolyte fuel cells performance

Water management in Polymer Electrolyte Fuel Cell (PEFC) is a key factor in fuel cell performance, and it is an important contributor to the proton exchange membrane durability. Water droplet accumulation in the channel causes non-uniform distribution of gas pressure and spatial inhomogeneity of the local current density in potentiostatic mode. These spatial and temporal fluctuations in the operating conditions imply unequal use of the membrane surface and the catalyst layer, producing uneven degradation and aging of the Membrane Electrode Assembly (MEA). In order to study the dynamic and spatial performance of the fuel cell, a three-level model has been developed. The model is composed of a two-phase, where steam and liquid water drops movement are considered in the channel model; liquid water and gas diffusion are considered in Gas Diffusion Layers (GDLs) model; and finally, the electrochemical reactions are represented in the electrochemical model. The complete model provides a wider understanding of the effect of water on PEFCs and allows to analyze the local current density and the water distribution in response to experimental set-up parameters such as anode and cathode gas flows, total current or channel geometries. The model has been validated using neutron images and segmented cells technique to evaluate the spatial distribution of liquid water and current density in the cell. The developed model and the simulation procedure proposed in this paper allow obtaining long-term dynamic simulations with low computational effort.     

Effect of flow field design on the performance of elevated-temperature polymer electrolyte fuel cells

In our previous work, operation of polymer electrolyte fuel cell (PEFC) at 95°C was investigated in detail and it was found that dry operation of PEFC at elevated temperatures makes the parallel flow field design a viable design option for high temperature applications such as for automobiles. In this work, a three-dimensional, non-isothermal PEFC model is used to compare the performance of a 25 cm² fuel cell with serpentine and parallel flow field design operated at 95°C under various inlet humidity conditions. Numerical results show that the parallel flow field provides better and more uniformly distributed performance over the whole active area which makes the parallel flow field a better design compared to the serpentine flow field for PEFCs operated at elevated temperature and low inlet relative humidity. Copyright © 2006 John Wiley & Sons, Ltd.     

The effects of water and microstructure on the performance of polymer electrolyte fuel cells

In this paper, we present a comprehensive non-isothermal, one-dimensional model of the cathode side of a Polymer Electrolyte Fuel Cell. We explicitly include the catalyst layer, gas diffusion layer and the membrane. The catalyst layer and gas diffusion layer are characterized by several measurable microstructural parameters. We model all three phases of water, with a view to capturing the effect that each has on the performance of the cell. A comparison with experiment is presented, demonstrating excellent agreement, particularly with regard to the effects of water activity in the channels and how it impacts flooding and membrane hydration. We present several results pertaining to the effects of water on the current density (or cell voltage), demonstrating the role of micro-structure, liquid water removal from the channel, water activity, membrane and gas diffusion layer thickness and channel temperature. These results provide an indication of the changes that are required to achieve optimal performance through improved water management and MEA-component design. Moreover, with its level of detail, the model we develop forms an excellent basis for a multi-dimensional model of the entire membrane electrode assembly.     

Numerical modeling of a non-flooding hybrid polymer electrolyte fuel cell

Experimental results were recently reported regarding a novel “non-flooding” hybrid fuel cell consisting of proton exchange membrane (PEM) and anion exchange membrane (AEM) half-cells on opposite sides of a water-filled, porous intermediate layer. Product water formed in the porous layer, where it could permeate to the exterior of the cell, rather than at the electrodes. Although electrode flooding was mitigated, the reported power output was low. To investigate the potential for increased power output, a physicochemical charge transport model of the porous electrolyte layer is reported here. Traditional electrochemical modeling was generalized in a novel way to consider both ion transport and reaction in the aqueous phase and electronic conduction in the graphitic scaffold using a unified Poisson–Nernst–Planck framework. Though the model used no arbitrary or fitting parameters, the ionic resistance calculated for the porous layer agreed well with the highly non-Ohmic experimental values previously reported for the entire fuel cell. Interestingly, electronic charge carriers in the scaffold were found to obviate the need for counterion presence in this unique electrolyte structure. Still, the thickness- and temperature-dependent model results offer limited prospects for improving the power output.