Evaluating the impact of V2G services on the degradation of batteries in PHEV and EV

Many researchers and industry observers claim that electric vehicles (EV) and plug-in hybrid electric vehicles (PHEV) could provide vehicle-to-grid (V2G) bulk energy and ancillary services to an electricity network. This work quantified the impact on various battery characteristics whilst providing such services. The sensitivity of the impact of V2G services on battery degradation was assessed for EV and PHEV for different battery capacities, charging regimes, and battery depth of discharge. Battery degradation was found to be most dependent on energy throughput for both the EV and PHEV powertrains, but was most sensitive to charging regime (for EVs) and battery capacity (for PHEVs). When providing ancillary services, battery degradation in both powertrains was most sensitive to individual vehicle battery depth of discharge. Degradation arising from both bulk energy and ancillary services could be minimised by reducing the battery capacity of the vehicle, restricting the number of hours connected and reducing the depth of discharge of each vehicle for ancillary services. Regardless, best case minimum impacts of providing V2G services are severe such as to require multiple battery pack replacements over the vehicle lifetime. © 2013 Elsevier Ltd.

The use of non-dimensional parameters to study stress in lithiumion battery electrode storage particles

Mechanical degradation is thought to be one of the causes of capacity fade within Lithium-Ion batteries. In this work we develop a coupled stress-diffusion model for idealized spherical storage particles, which is analogous to the development of thermal strains. We then non-dimensionalize the model and identify three important parameters that control the development of stress within these particles. We can therefore use a wide number of values for these parameters to make predictions about the stress responses of different materials. The maximum stress developed within the particle for different values of these parameters are plotted as stress maps. A two dimensional model of a battery was then developed, in order to study the effect of particle morphology. Copyright © 2012 by ASME.

An integrated 2-D model of a lithium ion battery: The effect of material parameters and morphology on storage particle stress

An integrated 2-D model of a lithium ion battery is developed to study the mechanical stress in storage particles as a function of material properties. A previously developed coupled stress-diffusion model for storage particles is implemented in 2-D and integrated into a complete battery system. The effect of morphology on the stress and lithium concentration is studied for the case of extraction of lithium in terms of previously developed non-dimensional parameters. These non-dimensional parameters include the material properties of the storage particles in the system, among other variables. We examine particles functioning in isolation as well as in closely-packed systems. Our results show that the particle distance from the separator, in combination with the material properties of the particle, is critical in predicting the stress generated within the particle. © 2012 Springer-Verlag.

Period Continuous Tuning of an Efficient Mid-Infrared Optical Parametric Oscillator Based on a Fan-out Periodically Poled MgO-Doped Lithium Niobate

We report a period continuously tunable, efficient, mid-infrared optical parametric oscillator (OPO) based on a fan-out periodically poled MgO-doped congruent lithium niobate (PPMgLN). The OPO is pumped by a Nd:YAG laser and a maximum idler output average power of 1.65 W at 3.93 mu m is obtained with a pump average power of 10.5 W, corresponding to the conversion efficiency of about 16% from the pump to the idler. The output spectral properties of the OPO with the fan-out crystal are analyzed. The OPO is continuously tuned over 3.78-4.58 mu m (idler) when fan-out periods are changed from 27.0 to 29.4 mu m. Compared with temperature tuning, fan-out period continuous tuning has faster tuning rate and wider tuning range.

聚合物锂离子电池和生物燃料电池的相关研究

本论文分为两个部分研究了铿离子电池和生物燃料电池中的关键材料，主要的创新点和结论如下。采用聚合物电解质是提高铿二次电池性能的有效方法之一。聚合物电解质良好电导率、高铿离子迁移数、宽电化学窗口以及好的机械性能是其应用于铿二次电池中的关键。论文的第一部分主要讨论了聚合物、增塑剂和无机纳米粒子等对复合电解质体系的化学和物理性质的影响。我们采用溶液浇注一浸渍法制备了各种纳米复合聚合物电解质，例如开发出基于PVDFHFP或梳状聚合物基体的全固态以及聚合物和碳酸醋形成的胶体聚合物电解质体系。首次制备了具有较高离子电导率的单离子聚合物电解质。考察了两类纳米粒子填充物对体系的影响：一种是“惰性”发烟硅；另一种是“活性”蒙脱土。比较了全固态和胶体聚合物电解质体系电化学性质的不同之处。采用电化学交流阻抗，示差扫描量热法，X衍射，拉曼光谱，红外光谱，扫描电镜，循环伏安等方法详细研究了聚合物电解质中各组分对体系离子电导率和机械性能的影响。研究结果表明，纳米复合物为开发具有特定电化学和机械性能的电解质提供了一种有效的途径，它对聚合物电解质的物理性质影响明显。纳米粒子的加入增强了体系的机械性能，同时也使体系对溶剂的吸附能力增加。在全固态聚合物电解质中加入增塑剂，形成胶体态聚合物电解质，体系的电导率大大增加。所制备的胶体复合物电解质的室温电导率可以达到10-3s cm-1的数量级，机械强度好，阳离子迁移数高。指出选择合适的添加剂及复合方法，控制界面的结构和形态，形成尽可能多的高导电的界面，是获得电导率高和机械性能良好的聚合物电解质的有效途径。并讨论了聚合物电解质在铿离子电池中的应用。 近年来，针对生物燃料电池的研究得到了广泛关注，其中实现蛋白质酶分子和电极之间的直接电子传递是研究中的热点。论文的第二部分主要研究了生物燃料电池中的酶电极。通过对碳纳米管（MWNTs）进行预处理，使其表面带有功能性官能团，从而可以实现酶分子在碳纳米管表面的固定，同时还保持了其生物活性。采用吸附法将微过氧化物酶-11（MP-11）或葡萄糖氧化酶（GOx）等生物分子固定到MWNTs上制成酶修饰电极，研究MWNTs对酶和电极之间电子传递的促进作用。当酶分子（MP-11，GOX）固定到MWNTs表面后，循环伏安结果显示出一对可逆的氧化还原峰，对应酶分子的直接电子转移。研究结果表明这种方法可以扩展到固定其他生物酶分子以及实现蛋白质酶分子和电极之间的直接电化学，可以获得一系列氧化还原酶分子的电化学参数，如反应速率常数等。同时，我们还研究了酶修饰电极对其底物的电催化反应。研究结果表明，该修饰电极对底物的电化学反应表现出较好的催化活性。我们还研究了酶分子在MWNTs修饰铂微电极上的电化学行为。这些研究为研制生物燃料电池提供了一种固定酶以及制备电极材料较好的方法。

PASSIVATION OF COPPER BY LITHIUM IN P-TYPE GAAS

We report the passivation of two deep copper-related acceptor levels in Cu-diffused p-type GaAs by the group-I element lithium. The deep-level-transient-spectroscopy (DLTS) signals of the well-known Cu-related levels with apparent activation energies 0.15 eV and 0.40 eV disappear in Cu-diffused samples when they are diffused with Li, but can be reactivated by annealing. Photoluminescence measurements show a corresponding disappearance and reappearance of the copper-related luminescence at 1.36 eV. Also we observe with DLT'S an energy level at E(V) + 0.32 eV in the Cu-Li-diff-used samples. The level is neither present in the Cu-diffused samples before Li diffusion nor in Cu-Li-diffused samples after annealing. As the level is not observed in starting materials or solely Li-diffused samples we suggest that it is related to a Cu-Li complex.

LITHIUM PASSIVATION OF ZN AND CD ACCEPTORS IN P-TYPE GAAS

We report lithium passivation of the shallow acceptors Zn and Cd in p-type GaAs which we attribute to the formation of neutral Li-Zn and Li-Cd complexes. Similar to hydrogen, another group-I element, lithium strongly reduces the concentration of free holes when introduced into p-type GaAs. The passivation is inferred from an increase of both the hole mobility and the resisitivity throughout the bulk of the sample. It is observed most clearly for Li concentrations comparable to the shallow-acceptor concentration. In addition, compensation of shallow acceptors by randomly distributed donors is present in varying degree in the Li-diffused samples. Unlike hydrogenation of n-type GaAs, Li doping shows no evidence of neutralizing shallow donors in GaAs.

Theoretical Study on Inner Shell Electron Impact Excitation of Lithium

Cross sections for electron impact excitation of lithium from the ground state 1s(2)2s to the excited states 1s2s(2), 1s2p(2), 1s2snp (n = 2-5), 1s2sns (n = 3-5), 1s2pns (n = 3-5), and 1s2pnp (n = 3-5) are calculated by using a full relativistic distorted wave method. The latest experimental electron energy loss spectra for inner-shell electron excitations of lithium at a given incident electron energy of 2500 eV [Chin. Phys. Lett. 25 (2008) 3649] have been reproduced by the present theoretical investigation excellently. At the same time, the structures of electron energy loss spectra of lithium at low incident electron energy are also predicted theoretically, it is found that the electron energy loss spectra in the energy region of 55-57 eV show two-peak structures.

Photoionization of 1s electron and corresponding shake-up process in ground and excited lithium atoms

The cross sections of the 18 electron photoionization and corresponding shake-up processes for Li atoms in the ground state 1s(2)2s and excited states 1s(2)2p, 1s(2)3p, 1s(2)3p and 1s(2)3d are calculated using the multi-configuration Dirac-Fock method. The latest experimental photoelectron spectrum at hv = 100 eV [Cubaynes D et al. Phys. Rev. Lett. 99 (2007) 213004] has been reproduced by the present theoretical investigation excellently. The relative intensity of the shake-up satellites shows that the effects of correlation and relaxation become more important for the higher excited states of the lithium atom, which are explained very well by the spatial overlap of the initial and final state wavefunctions. In addition, strong dependence of the cross section on the atomic orbitals of the valence electrons are found, especially near the threshold.

Preparation of Microporous Membranes by Swift Heavy Ion Irradiation and Impedance Characterization

Polypropylene (PP) microporous membranes were successfully prepared by swift heavy ion irradiation and track-etching. Polypropylene foils were irradiated with Au-197 ions of kinetic energy 11.4 MeV.u(-1) (total energy of 2245.8 MeV) and fluence 1x10(8) ions.cm(-2) at normal incidence. The damaged regions produced by the gold ions along the trajectories were etched in H2SO4 and K2Cr2O7 solutions leading to the formation of cylindrical pores in the membranes. The pore diameters of the PP microporous membranes increased from 380 to 1610 nm as the etching time increased from 5 to 30 min. The surface and cross-section morphologies of the porous membranes were characterized by scanning electron microscopy (SEM). The micropores in the membranes were found to be cylindrical in shape, homogeneous in distribution, and equal in size. Some mathematical relations of the porosity of the PP microporous membranes were established by analytic derivation. The microporous membranes were used in lithium-ion batteries to measure their properties as separators. The electrical conductivity of the porous membrane immersed in liquid electrolyte was found to be comparable to that of commercial separators by electrochemical impedance spectroscopy (EIS). The results showed that the porosity and electrical conductivity were dependent on the ion fluence and etching time. By adjusting these two factors, microporous membranes with good porosity and electrical conductivity were made that met the requirements for commercial use.

利用重离子辐照技术制备锂离子电池隔膜；Preparation Lithium-ion Battery Separator by Swift Heavy Ion Irradiation Methods

用能量11.4MeV/u和注量1×108ions/cm2的197Au离子垂直辐照聚丙烯薄膜,通过电导测量法监测温度、硫酸浓度和重铬酸钾浓度对径迹蚀刻速率的影响,得到合适的蚀刻条件;成功制备出孔径范围在600—1000nm的重离子径迹聚丙烯孔膜,并用场发射扫描电镜对孔的形状及孔径大小进行了表征,对孔洞锥角的形成进行了分析,为重离子辐照技术制备锂离子电池隔膜提供了实验数据。