Electrospun polymer membrane activated with room temperature ionic liquid: Novel polymer electrolytes for lithium batteries

A new class of polymer electrolytes (PEs) based on an electrospun polymer membrane incorporating a room-temperature ionic liquid (RTIL) has been prepared and evaluated for suitability in lithium cells. The electrospun poly(vinylidene fluoride-co-hexafluoropropylene) P(VdF-HFP) membrane is activated with a 0.5 M solution of LiTFSI in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI) or a 0.5 M solution of LiBF₄ in 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF₄). The resulting PEs have an ionic conductivity of 2.3 × 10⁻³ S cm⁻¹ at 25 °C and anodic stability at >4.5 V versus Li⁺/Li, making them suitable for practical applications in lithium cells. A Li/LiFePO₄ cell with a PE based on BMITFSI delivers high discharge capacities when evaluated at 25 °C at the 0.1C rate (149 mAh g⁻¹) and the 0.5C rate (132 mAh g⁻¹). A very stable cycle performance is also exhibited at these low current densities. The properties decrease at the higher, 1C rate, when operated at 25 °C. Nevertheless, improved properties are obtained at a moderately elevated temperature of operation, i.e. 40 °C. This is attributed to enhanced conductivity of the electrolyte and faster reaction kinetics at higher temperatures. At 40 °C, a reversible capacity of 140 mAh g⁻¹ is obtained at the 1C rate.     

石墨烯/碳纳米管/环氧树脂复合材料的导热性能的实验研究

在微电子领域中,随着元器件的体积微小化,要求导热材料具备体积小、高导热的特点。高分子导热复合材料能很好的解决器件在不同的工作环境中仍能保持正常的散热问题。以环氧树脂(EP)为基体,石墨烯粉末(GP)和多壁碳纳米管(MWCNTs)为导热填料,采用溶剂和超声分散法,制备出石墨烯/碳纳米管/环氧树脂复合材料。实验采用瞬态电热技术测量其导热系数,结果显示,石墨烯与碳纳米管协同作为导热填料时,复合材料导热性优于单独添加导热填料(GP或MWCNTs),且随着GP所占比例的增大复合材料的导热系数越大。当GP和MWCNTs比例分别为0.7%和0.3%时,复合材料导热系数为0.940 W/(m·K),相比于纯EP导热系数提高了286.83%。     

Good prospect of ionic liquid based-poly(vinyl alcohol) polymer electrolytes for supercapacitors with excellent electrical,electrochemical and thermal properties

Poly(vinyl alcohol) (PVA)/ammonium acetate (CH₃COONH₄)/1–butyl–3–methylimidazolium chloride (BmImCl) based polymer electrolytes were prepared by solution casting method. The ionic conductivity increased with temperature as shown in temperature dependent-ionic conductivity study. The maximum ionic conductivity of (7.31 ± 0.01) mS cm⁻¹ was achieved at 120 °C upon adulteration of 50 wt% of BmImCl. The samples obeyed Vogel–Tamman–Fulcher (VTF) relationship. The glass transition temperature (T_g) of the polymer matrix was reduced by doping it with salt and ionic liquid as shown in differential scanning calorimetry (DSC). Supercapacitor was thus assembled. Wider potential stability range has been observed with addition of ionic liquid. Inclusion of ionic liquid also improved the electrochemical behavior of EDLC. The capacitance of supercapacitor were determined by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge–discharge tester. The cell also illustrated energy density of 2.39 Wh kg⁻¹ and power density of 19.79 W kg⁻¹ with Coulombic efficiency above 90%.     

Thermal conductivity and temperature profiles of the micro porous layers used for the polymer electrolyte membrane fuel cell

The thermal conductivity and the thickness change with pressure of several different micro porous layers (MPL) used for the polymer electrolyte membrane fuel cell (PEMFC) were measured. The MPL were made with different compositions of carbon and polytetrafluoroethylene (PTFE). A one-dimensional thermal PEMFC model was used to estimate the impact that the MPL has on the temperature profiles though the PEMFC.     

Enhanced ionic conductivity of yttria-stabilized ZrO2 with natural CuFe-oxide mineral heterogeneous composite for low temperature solid oxide fuel cells

We report for the first time that the commercial yttrium stabilized zirconia (YSZ) nanocomposite with a natural CuFe-oxide mineral (CF) exhibits a greatly enhanced ionic conductivity in the low temperature range (500–600 °C), e.g. 0.48 S/cm at 550 °C. The CF–YSZ composite was prepared via a nanocomposite approach. Fuel cells were fabricated by using a CF–YSZ electrolyte layer between the symmetric electrodes of the Ni_0.8Co_0.2Al_0.5Li (NCAL) coated Ni foam. The maximum power output of 562 mW/cm² has been achieved at 550 °C. Even the CF alone to replace the electrolyte the device reached the maximum power of 281 mW/cm² at the same temperature. Different ion-conduction mechanisms for YSZ and CF–YSZ are proposed. This work provides a new approach to develop natural mineral composites for advanced low temperature solid oxide fuel cells with a great marketability.     

Electrochemical performance of gel polymer electrolyte with ionic liquid and PUA/PMMA prepared by ultraviolet curing technology for lithium-ion battery

A series of diethylethyletherylmethanamine bis(trifluoromethanesulfonyl)imide (DEEYTFSI) ionic liquid gel polymer electrolyte based polyurethane acrylate (PUA)/poly(methyl methacryltae) (PMMA) matrix with different contents of DEEYTFSI, PUA and LiTFSI were prepared via ultraviolet (UV) curing system. Electrochemical performances of the gel polymer were studied by electrochemical station and charge–discharge system. The gel polymer electrolyte with 19 wt.% DEEYTFSI obtained a maximum conductivity σ of 2.76 × 10^?4 S cm^?1 and the transference number t_Li+ of ～0.22 at room temperature. 19 wt.% DEEYTFSI caused the easier transferring of lithium ions due to less apparent activation energy E_a of 21.1 kJ mol^?1. The DEEYTFSI/LiTFSI/PUA/PMMA electrolyte had good compatibility with LiFePO₄ cathode. The DEEYTFSI/LiTFSI/PUA/PMMA electrolyte with the electrochemical window of 4.70 V was enough stability for being the electrolyte material of lithium battery. The Li/19 wt.% DEEYTFSI–LiTFSI–PUA–PMMA/LiFePO₄ coin-typed cell cycled at 0.1 C presented 95% efficiency on the 50th cycle.     

Low energy ion beam assisted deposition of controllable solid state electrolyte LiPON with increased mechanical properties and ionic conductivity

Lithium phosphorus oxynitride (LiPON) solid state amorphous film electrolytes were synthesized by ion beam assisted deposition (IBAD) using Li₃PO₄ target under nitrogen reactive plasma. IBAD presents an advantage of controllable nitrogen content of the films by adjusting N₂ and Ar flow ratio. X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), nanoindenter, and profiler were employed to characterize LiPON films. Our results indicate that the film at N₂ and Ar flow ratio of 1:8 showed the best surface morphology and mechanical properties. The highest N atomic percentage of 2.32% was also obtained at this synthesis circumstance, and the resultant LiPON film electrolyte showed higher ionic conductivity of 4.5 × 10⁻⁶ S/cm at room temperature, as well as the highest hardness of 6.8 GPa and the lowest compressive stress of 147.2 MPa. It is believed that as-prepared LiPON solid state electrolyte film optimized can effectively prevent delamination from electrodes, showing some promising application in thin film lithium ion batteries.     

Classical and minimum entropy generation analyses for steady state conduction with temperature dependent thermal conductivity and asymmetric thermal boundary conditions: Regular and functionally graded materials

Minimum entropy generation (MEG) temperature profiles are derived for steady conduction in a plane wall, a hollow cylinder and a hollow sphere and compared with the classical results. Cases of constant thermal conductivity, temperature dependent and location dependent thermal conductivities for each geometry are analyzed. Results are presented for the classical and the minimum entropy temperature profiles illustrating the effect of thermal asymmetry and variable thermal conductivity in each geometry. These results show that the difference between the classical and the MEG temperature profiles is largest when there is a strong thermal asymmetry. For all three geometries, the effect of temperature dependent thermal conductivity on the classical temperatures is moderate but its effect on the MEG temperatures is only small. Both the classical and minimum entropy generation rates, for each geometry, are found to be strong functions of thermal asymmetry and thermal conductivity variation parameter. Comparison of results for a hollow cylinder and a hollow sphere reveals that rate of entropy generation in a hollow sphere is much higher than in a hollow cylinder for the same thermal asymmetry and radius ratio.     

Preparation of Pt/zeolite–Nafion composite membranes for self-humidifying polymer electrolyte fuel cells

A novel Pt/zeolite–Nafion (PZN) polymer electrolyte composite membrane is fabricated for self-humidifying polymer electrolyte membrane fuel cells (PEMFCs). A uniform dispersion of Pt nanoparticles with an average size of 3 nm is achieved by ion-exchange of the zeolite HY. The Pt nanoparticles embedded in the membrane provide the catalytic sites for water generation, whereas the zeolite HY-supported Pt particles absorbs water and make it available for humidification during cell operation at elevated temperature. Compared with the performance of ordinary membranes, the performance of cells with PZN membranes is improved significantly under dry conditions. With dry H₂ and O₂ at 50 °C, the PZN membrane with 0.65 wt.% of Pt/zeolite (0.03 mg Pt cm⁻²) gives 75% of the performance obtained at 0.6 V with the humidified reactants at 75 °C. Impedance analysis reveales that an increase in charge-transfer resistance is mainly responsible for the cell performance loss operated with dry gases.     

Lattice thermal conductivity of Si/Ge composite thermoelectric material: Effect of Si particle distribution

Embedding nanoparticles (NPs) in a matrix can effectively enhance the phonon scattering by the interface, reduce the lattice thermal conductivity, and improve the thermoelectric properties of the material. However, the understanding of how the distribution of embedded NPs affects the thermal conductivity is still not clear. To explore the underlying mechanism, frequency‐dependent Monte Carlo simulation and the effective medium method are applied to study the lattice thermal conductivity of Si/Ge composite (Si NPs embedded in Ge matrix). The effect of the free path distribution (FPD) of Ge phonon induced by the heterogeneous distribution of Si NPs is introduced into the effective medium method, and then, this method is used to calculate the lattice thermal conductivity of Si/Ge composite when Si NPs are unevenly distributed. Results show that decreasing the separation distance of adjacent NPs can slightly decrease the lattice thermal conductivity. Assuming that the FPD of Ge phonon induced by Si‐Ge interface scattering obeying lognormal distribution and that the deviation σ indicates the degree of inhomogeneity of Si NPs distribution, lattice thermal conductivity of composites with different σ is obtained. It is found that lattice thermal conductivity significantly decrease by more than 40%, with the increase of σ, especially for high‐Si concentrations. The present study indicates that the particle distribution in a composite can markedly affect the lattice thermal conductivity.     

强化导热相变材料对PV/PCM热控特性影响研究

文章建立了光伏/相变材料(PV/PCM)太阳能热控系统二维模型,并根据模拟结果研究了相变材料热导率对太阳电池热控特性的影响。模拟结果表明,当PCM热导率由0.3 W/(m·K)逐渐增加至1.1 W/(m·K)时,相变材料对太阳电池的热控效果越来越好。此外,文章设计了PCM热导率分别为0.8,1.1 W/(m·K)的PV/PCM太阳能热控系统实验装置,在模拟光源和自然光条件下,对太阳能热控系统实验装置的输出功率以及太阳电池的温度进行测试。实验结果表明:在模拟光源下,与无PCM太阳电池相比,PCM热导率分别为0.8,1.1 W/(m·K)的太阳电池的最高温度分别降低了4.6,10.8℃,平均输出功率分别提高了2.2%,4.1%;在自然光条件下,与无PCM太阳电池相比,PCM热导率分别为0.8,1.1 W/(m·K)的太阳电池的最高温度分别降低了9.7,12℃,平均输出功率分别提高了3.1%,5.98%。     

Determination of temperature distribution for annular fins with temperature‐dependent thermal conductivity

In this paper, homotopy analysis method (HAM) has been used to evaluate the temperature distribution of annular fin with temperature‐dependent thermal conductivity and to determine the temperature distribution within the fin. This method is useful and practical for solving the nonlinear heat transfer equation, which is associated with variable thermal conductivity condition. HAM provides an approximate analytical solution in the form of an infinite power series. The annular fin heat transfer rate with temperature‐dependent thermal conductivity has been obtained as a function of thermo‐geometric fin parameter and the thermal conductivity parameter describing the variation of the thermal conductivity. © 2011 Wiley Periodicals, Inc. Heat Trans Asian Res; Published online in Wiley Online Library ( wileyonlinelibrary.com/journal/htj ). DOI 10.1002/htj.20353     

The effects of hydrogen addition,inlet temperature and wall thermal conductivity on the flame-wall thermal coupling of premixed propane/air mixtures in meso-scale tubes

The effects of hydrogen addition, inlet temperature, wall thermal conductivity and wall thickness on the flame-wall coupling of the propane/air flames in a meso-scale tube are numerically investigated using a two dimensional model along with the detailed chemical mechanism. Higher wall thermal conductivity can result in preheating the fresh mixture uniformly in strongly flame-wall coupled system, which is vital to enhance the burning rate of fuel mixture. With the increase of wall thermal conductivity or hydrogen addition, the leading edge of the flame shifts from the wall to the axis, meanwhile the flame is more convex towards the unburned side near the leading edge. As the hydrogen addition and inlet temperature increase, the flame propagation speed increases significantly, while the maximum temperature and maximum total enthalpy decrease due to the reduced heat recirculation power. The flame propagation speed has a negative correlation with heat loss. The chemical reactions in preheat zone are enhanced at low wall thermal conductivity due to the higher inner wall temperature. Thinner combustor wall leads to higher flame speed and higher heat loss simultaneously. Results have implications on the choice of solid wall material and heat recirculation design in a stable meso-scale combustor for different fuels.     

Computational fluid dynamic and thermal stress analysis of coatings for high‐temperature corrosion protection of aerospace gas turbine blades

The current investigation presents detailed finite‐element simulations of coating stress analysis for a three‐dimensional, three‐layered model of a test sample representing a typical gas turbine component. Structural steel, titanium alloy, and silicon carbide are selected for main inner, middle, and outermost layers respectively. ANSYS is used to conduct three types of analysis—static structural, thermal stress analysis, and also computational fluid dynamic erosion (via ANSYS FLUENT). The specified geometry, which corresponds to corrosion test samples exactly, is discretized using a body‐sizing meshing approach, comprising mainly of tetrahedron cells. Refinements were concentrated at the connection points between the layers to shift the focus toward the static effects dissipated between them. A detailed grid independence study is conducted to confirm the accuracy of the selected mesh densities. The momentum and energy equations were solved, and the viscous heating option was applied to represent the improved thermal physics of heat transfer between the layers of the structures. A discrete phase model (DPM) in ANSYS FLUENT was used, which allows for the injection of continuous uniform air particles onto the model, thereby enabling an option for calculating the corrosion factor caused by hot air injection. Extensive visualization of results is provided. The simulations show that ceramic (silicon carbide) when combined with titanium clearly provide good thermal protection; however, the ceramic coating is susceptible to cracking and the titanium coating layer on its own achieves significant thermal resistance. Higher strains are computed for the two‐layer model than the single layer model (thermal case). However even with titanium only present as a coating the maximum equivalent elastic strain is still dangerously close to the lower edge. Only with the three‐layer combined ceramic and titanium coating model is the maximum equivalent strain pushed deeper towards the core central area. Here the desired effect of restricting high stresses to the strongest region of the gas turbine blade model is achieved, whereas in the other two models, lower strains are produced in the core central zones. Generally, the CFD analysis reveals that maximum erosion rates are confined to a local zone on the upper face of the three‐layer system which is in fact the sacrificial layer (ceramic coating). The titanium is not debonded or damaged which is essential for creating a buffer to the actual blade surface and mitigating penetrative corrosive effects. The present analysis may further be generalized to consider three‐dimensional blade geometries and corrosive chemical reaction effects encountered in gas turbine aero‐engines.     

Improvement of cell performance in catalyst layers with silica-coated Pt/carbon catalysts for polymer electrolyte fuel cells

Carbon-supported Pt catalysts (Pt/Cs) for use of cathode catalyst layers (CLs) for PEFCs were covered with silica layers in order to improve performance. CLs with low ratio of ionomer to carbon (I/C) for Pt/C and silica-coated Pt/C were fabricated using an inkjet printing (denoted as Pt/C(IJ) and SiO₂-Pt/C(IJ)) to reduce oxygen diffusion resistance. Compared to Pt/C(IJ), SiO₂-Pt/C(IJ) ink maintained good dispersion and high stability under the lower I/C. The performance of SiO₂-Pt/C(IJ) was significantly higher than Pt/C(IJ) at 0.6 V under all humidity conditions. In particular, the performance of SiO₂-Pt/C(IJ) under low humidity conditions showed noticeable improvement regardless of current density area. From FIB-SEM, it was confirmed that the morphologies and porosities of both catalysts were the same. Thus, these results indicate that oxygen diffusion resistance, related to structure of CLs, hardly affects the performance, whereas improved performance is attributed to increased proton conductivity by silica layers containing hydrophilic groups.     

Screening of novel water/ionic liquid working fluids for absorption thermal energy storage in cooling systems

Absorption thermal energy storage (ATES) is significant for renewable/waste energy utilization in buildings. The ATES systems using ionic liquids (ILs) are explored to avoid crystallization and enhance the performance. Property model and cycle model have been established with verified accuracies. Based on the preliminary screening, seven ILs are found feasible to be ATES working fluids, while four ILs ([DMIM][DMP], [EMIM][Ac], [EMIM][DEP], and [EMIM][EtSO₄]) have been selected for detailed comparisons. The coefficient of performance (COP) and energy storage density (ESD) of the ATES using different H₂O/ILs are compared with H₂O/LiBr. Results show that the operating temperatures of LiBr are constrained by crystallization, limiting the COPs and ESDs under higher generation temperatures and lower condensation temperatures. With varying T_g, [DMIM][DMP] yields higher COPs with T_g above 100°C and [EMIM][Ac] yields comparable ESDs (67.7 vs 67.1 kWh/m³) with T_g around 120°C, as compared with LiBr. The maximum COP is 0.745 for [DMIM][DMP]. With varying T_c, [DMIM][DMP] yields higher COPs with T_c below 38°C and [EMIM][Ac] yields higher ESDs with T_c below 33°C, as compared with LiBr. The maximum ESD is 87.5 kWh/m³ for [EMIM][Ac]. With varying T_e, [DMIM][DMP] yields higher COPs with T_e above 8°C, as compared with LiBr. The maximum ESD of ILs is 104.0 kWh/m³ for [EMIM][EtSO₄]. Comparing with the volume-based ESDs, the differences between ILs and LiBr are smaller for the mass-based ESDs. This work can provide suggestions for the selection of novel working fluids for ATES for performance and reliability enhancement.     

Preparation and electrochemical characterization of polymer electrolytes based on electrospun poly(vinylidene fluoride-co-hexafluoropropylene)/polyacrylonitrile blend/composite membranes for lithium batteries

Apart from PEO based solid polymer electrolytes, tailor-made gel polymer electrolytes based on blend/composite membranes of poly(vinylidene fluoride-co-hexafluoropropylene) and polyacrylonitrile are prepared by electrospinning using 14 wt% polymer solution in dimethylformamide. The membranes show uniform morphology with an average fiber diameter of 320-490 nm, high porosity and electrolyte uptake. Polymer electrolytes are prepared by soaking the electrospun membranes in 1 M lithium hexafluorophosphate in ethylene carbonate/dimethyl carbonate. Temperature dependent ionic conductivity and their electrochemical performance are studied. The blend/composite polymer electrolytes show good ionic conductivity in the range of 10⁻³ S cm⁻¹ at ambient temperature and good electrochemical performance. All the Polymer electrolytes show an anodic stability >4.6 V with stable interfacial resistance with storage time. The prototype cell shows good charge-discharge properties and stable cycle performance with comparable capacity fade compared to liquid electrolyte under the test conditions.     

Experimental investigation of thermal management system for lithium ion batteries module with coupling effect by heat sheets and phase change materials

Some potential safety risks for lithium ion battery such as overheating, combustion, and explosion occurred in practical application may cause accidents of electric vehicles. Phase change material (PCM)‐based thermal management system was demonstrated as a feasible approach. However, the batteries have to endure various environment and climate, which would not work normally under cold area. Especially when the surrounding temperature falls to below 10°C, which can bring about the energy and power of Li‐ion batteries rapidly reducing. In this study, a coupling heating strategy of the PCM‐based batteries module with 2 heat sheets at low temperature was proposed for batteries module and cannot only balance the temperature among different batteries in the module but also ensure to pre‐heat the batteries module at low temperature. The experiment displayed that 7% of EG in paraffin‐based composite PCMs was the best proportion for batteries module, considering both fluidity and thermal conductivity factors. In addition, the temperature difference of PCM‐based batteries module was 2.82°C, while that of the air‐based one was 14.49°C, which was 5 times more than former, exhibiting an excellent performance in balancing temperature uniformly, and was beneficial for prolonging the lifespan of batteries. The coupling heating strategy‐based PCM with heat sheets provided as an extremely promising technology for lithium batteries module at low temperature.     

A novel organic/inorganic composite solid electrolyte with functionalized layers for improved room‐temperature rate performance of solid‐state lithium battery

High ionic conductivity at room temperature (RT) and good ion transport capability at electrode/electrolyte interface are fundamental requirements for high‐rate solid‐state lithium batteries (SSBs). In this work, we designed a poly (propylene carbonate) (PPC)‐based organic/inorganic composite solid electrolyte (CSE) membrane with high filling of tantalum‐doped lithium lanthanum zirconium oxide (LLZTO) and functionalized layers for enhancing the RT rate performance of SSB. The synergistic effect of LLZTO and interfacial functionalized layers endows the NCM622/CSE/Li battery with high‐rate and cycling performances at RT. The SSB with 20% LLZTO‐filled solid electrolyte shows the initial capacities of 162.0, 148.5 and 130.1 mAh g^?1 at 1C, 2C, and 3C respectively, with retention capacities of 115.6, 104, and 100.6 mAh g^?1 after 150 cycles. This strategy for an organic/inorganic CSE is of great practical significance for the development of high‐rate SSBs.