ZIF-8复合PEO基固态电解质的制备与改性研究北大核心CSCD

在聚环氧乙烷(PEO)基固体聚合物电解质中加入无机填料,是一种低成本、有效改善其力学和电化学性能的方法。为了更有效地改善PEO基固态电解质的电化学性能,本工作采用流延法制备了纳米沸石咪唑骨架材料(ZIF-8)与聚氧化乙烯(PEO)复合的固态电解质。通过扫描电子显微镜(SEM)、X射线衍射(XRD)等物理表征和电化学阻抗谱(EIS)、伏安线性扫描(LSV)、充放电循环等电化学测试手段,证明了加入20%ZIF-8纳米粒子的PEO基复合固态电解质CPE20具有最小的体电阻、较宽的电化学稳定窗口与最低的活化能(8.4×10^(-3)eV);20℃时,其电导率达到了4.9×10^(-5)S/cm(比纯PEO高一个数量级);70℃时,其电导率为1.08×10^(-3)S/cm(与液态电解液相当);CPE20的锂离子迁移数提高至0.46,而纯PEO基固态电解质为0.36;采用CPE20制备的LiFePO_(4)||Li电池在室温下具有良好的容量和循环性能,而且容量保持率超过96%。加入适量的惰性填料ZIF-8时,可以有效降低聚合物的结晶度,增加聚合物的非晶区,促进锂盐的溶解,提高锂离子的迁移率,使复合固态电解质具有更加优异的电化学性能。因此添加ZIF-8的PEO基固相聚合物在固态金属锂电池中具有广阔的应用前景。     

新型PEO/LPOS复合聚合物电解质的制备与性能研究

将具有较高电导率和稳定性的硫化物电解质LPOS引入PEO基聚合物中,制备一种新型PEO/LPOS复合聚合物电解质。研究结果表明,1%LPOS的添加能显著改善PEO基聚合物电解质的电导率、锂离子迁移数和电化学稳定性。与纯PEO基电解质相比,新制备的复合聚合物电解质PEO18-LiTFSI-1%LPOS室温电导率由   6.18×106 S/cm提高至1.60×105 S/cm,提高了158%。80 ℃表现出最佳电导率为1.08×103 S/cm,电化学窗口提高至4.7 V,同时具有非常良好的对锂稳定性。以新型复合电解质组装的LiFePO4/Li全固态锂电池表现出良好的循环稳定性,在60 ℃ 1 C下循环50周后放电比容量仍维持在105 mA•h/g以上。     

LiI-Urea二元离子液体基电解质导电性能研究

简单配位合成LiI-Urea二元离子液体并向其中添加第三组分I2得到二元离子液体基电解质.采用FITR和紫外分光光度计表征了离子液体的结构及电解质的组成.采用线性扫描伏安法测试了电解质中I-3的极限电流密度,以此计算得到I-3的扩散系数.测试了电解质的电导率,探讨了电解质的组成与电导率之间的关系.结果表明,LiI/Urea的配比影响两组分之间的络合作用,从而影响I-3的扩散系数及电解质的电导率.室温下,两组分的摩尔比为n(LiI/Urea) =0.225时,I-3的扩散系数为2.29×10-6cm2·s-1,电导率达到2.63×10-3 S·cm-1,满足染料敏化太阳电池实用要求.     

PEO基Li_(1.5)Al_(0.5)Ge_(1.5)(PO_4)_3固体复合电解质的制备

以聚环氧乙烷(PEO)为黏结剂,离子导电性的Li1.5Al0.5Ge1.5(PO4)3(LAGP)为主相,乙腈为溶剂,按照EO/Li,摩尔比为13,变化Li N(CF3SO2)2(Li TFSI)中Li+与LAGP中Li+的比例,通过溶液浇注法制备得到LAGP-PEO(Li TFSI)固体复合电解质。用X射线衍射、扫描电镜(SEM)和电化学阻抗(EIS)等方法对固体复合电解质的形貌、结构和电导率进行表征。结果表明,LAGP可与PEO(Li TFSI)部分络合并均匀分散于PEO(LITFSI)内,整个体系内存有三个主体相,即PEO(Li TFSI)的复合相、LAGP晶相以及PEO与两种锂盐的过渡相。通过阻抗谱图发现,当质量比w(LAGP)∶w(PEO)=6∶4时,LAGP-PEO(Li TFSI)固体复合电解质具有最高的室温电导率,为2.68×10?5 S/cm,在333 K时,达到1.86×10?4 S/cm,接近LAGP的电导率水平。这说明固体复合电解质中加入LAGP即降低了PEO的结晶度,LAGP自身的电导率也有一定贡献。     

冠醚掺杂的聚合物固态电解质对全固态锂电池性能的影响北大核心CSCD

聚氧化乙烯(PEO)基固态电解质由于高的柔韧性、优异的加工性以及良好的界面兼容性等在全固态锂电池中极具应用前景,但其较低的室温离子电导率和较窄的电化学窗口限制了其高效应用。本工作采用溶液浇铸法将含有极性官能团的冠醚(15-C-5)分子分散在PEO/双三氟甲基磺酰亚胺锂(LiTFSI)基质中制备PEO/15-C-5聚合物固态电解质。重点探究冠醚含量对固态电解质中Li+传递的影响,同时对聚合固态电解质的形貌、力学性能、电化学性能进行系统研究。结果表明:10%15-C-5在PEO中分散性较好,可有效降低PEO的结晶度,进而提升PEO链段运动性,使其抗拉强度达1.83 MPa。15-C-5与锂离子间强的络合作用促进锂盐解离,同时对阴离子产生静电排斥,从而增强离子电导率并提高锂离子迁移数,30℃下离子电导率达到1.00×10^(-5)S/cm,60℃下锂离子迁移数达到0.42,分别是PEO电解质的4.5和1.9倍。另外冠醚与阴离子形成的静电排斥中心易捕获锂离子形成较为稳定的悬停位点,降低了PEO链段形成的O-Li络合活性位点促进C-O-C结构分解的可能性,从而提高PEO电解质的分解电压(从4.29 V到5.42 V)。与镍钴锰三元正极匹配的全固态锂电池展现出稳定的长循环性能,其在60℃、0.5 C的条件下初始放电比容量达到159 mAh/g,经100圈循环之后容量保持率达到89%。与磷酸铁锂正极匹配组装的全固态锂电池同样表现出优异的性能。     

新型固态聚合物电解质在锂硫电池中的性能研究

本工作采用（氟磺酰）（三氟甲基磺酰）亚胺锂{Li[(FSO2)(CF3SO2)N],LiFTFSI}和聚氧乙烯（PEO）分别作为导电锂盐和聚合物主链,通过简单的溶液浇铸法制备了新型固态聚合物电解质（SPEs）,并采取示差扫描量热（DSC）、热重（TGA）、线性扫描伏安（LSV）、交流阻抗（EIS）和恒电位直流（DC）极化等方法研究了LiFTFSI/PEO （EO/Li+摩尔比为16）电解质的理化性质和电化学性质。结果表明,LiFTFSI/PEO电解质具有较高的室温离子电导率（σ ≈10−5 S/cm）,较高的氧化电位（4.63 V vs. Li/Li+）,并且耐热温度高达256 ℃。锂硫电池测试结果表明,该类SPEs展现出相对高的首周放电比容量（881 mA•h/g）,有效地抑制了多硫离子的“穿梭效应”,表现出良好的电池循环性能。     

Mo,Al掺杂的Li_(7)La_(3)Zr_(2)O_(12)基复合固态电解质的制备及全固态电池性能研究北大核心CSCD

通过固态电解质构建的全固态锂离子电池具有极高的安全性及可靠性,是目前锂离子电池领域的研究热点。其中复合固态电解质既改善了聚合物电解质力学性能差、离子电导率低等缺点又解决了无机固态电解质的界面接触等问题。本文通过溶胶-凝胶法制备了掺杂了Al、Mo的Li_(7)La_(3)Zr_(2)O_(12)粉体,并将其与PEO(聚环氧乙烷)复合,利用溶液浇筑法制备了不同比例的复合固态电解质,考察其在全固态电池中的性能。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、差示扫描量热仪(DSC)等测试手段对Li_(6.65)Al_(0.05)La_(3)Zr_(1.9)Mo_(0.1)O_(12)粉体以及复合固态电解质进行了材料表征。同时利用电化学工作站、电池充放电测试系统测试了复合固态电解质在全固态电池中的应用性能。与纯PEO电解质相比,复合15%Li_(6.65)Al_(0.05)La_(3)Zr_(1.9)Mo_(0.1)O_(12)的电解质电化学窗口为4.79V,可以在0.2mA/cm^(2)下稳定循环500h,在0.1C倍率下,循环100圈容量保持率为89.9%。     

PEO/PS/PMMA聚合物电解质膜的制备及性能研究

聚合物电解质是解决锂离子电池安全性问题的有效途径之一。考察了由聚环氧乙烷(PEO)、聚苯乙烯(PS)、聚甲基丙烯酸甲酯(PMMA)、聚乙二醇(PEG)和双三氟甲烷磺酰亚胺锂盐(LiTFSI)组成的固体聚合物电解质膜的性能。采用聚合物共混技术制备了一系列复合聚合物电解质膜,通过扫描电子显微镜(SEM)和X射线衍射(XRD)对膜的形态和晶体结构进行了分析,并详细考察了离子电导率、孔隙率和吸液率等性能。PS和PMMA的加入降低了PEO的结晶度,提高了它的拉伸强度。结果表明,当PEO/PS/PMMA膜中各组成质量比为75:10:15时,聚合物电解质膜具有优良的性能,膜的离子电导率为3.56×10^-4S·cm^-1,拉伸强度为11.56MPa,孔隙率达到57.6%,吸液率高达164.3%。     

锂电池用全固态聚合物电解质的研究进展

目前大规模商业化的锂二次电池普遍采用有机碳酸酯类的液态电解质,易泄露、易燃烧、易爆炸等安全问题限制了该类电解质的进一步应用。全固态聚合物电解质（all-solid-state polymer electrolytes,ASPEs）电池具有安全性能好、能量密度高、工作温度区间广、循环寿命长等优点,是锂离子电池领域的研究热点之一。ASPEs通常还具有优异的力学性能,可以很好地抑制锂金属电极在充放电过程中的枝晶生长,所以在锂金属电池领域也具有十分重要的应用前景。作者综述了研究较多的几种ASPEs体系,包括聚氧化乙烯（PEO）基体系、聚碳酸酯基体系、聚硅氧烷基体系、聚合物锂单离子导体体系。PEO基ASPEs是研究最早且研究最多的一类ASPEs材料,但其高结晶性造成室温Li+迁移困难、离子电导率低等问题,所以研究人员研发了一系列降低PEO结晶度、提升体系离子电导率的改性手段。聚碳酸酯基ASPEs主链结构中含有强极性碳酸酯基团而且室温无定形态,使得锂盐更容易解离,且室温离子电导率一般较PEO基要高,是比较有潜力的PEO基ASPEs替代材料。除了碳链聚合物,玻璃化转变温度较低的聚硅氧烷基ASPEs体系也因为其较高的离子电导率受到研究人员关注。在锂电池充放电过程中,Li+才是有效载荷子,电解质中阴离子的迁移会增加电解质体系的浓差极化,所以阴离子不发生迁移、Li+迁移数接近于1的聚合物锂单离子导体也是一类具有研究价值的ASPEs材料。最后,本综述讨论了全固态聚合物电解质的应用前景及未来发展方向,指出了PEO基体系的研究重点在于发展有机-无机复合体系、聚碳酸酯基体系的研究重点在于发展与其它聚合物的共混体系、聚硅氧烷基体系的研究重点在于增强体系力学性能、聚合物锂单离子导体体系的研究重点在于设计离子电导率更高的新型聚阴离子锂盐。     

锂盐对LAGP-PEO复合固体电解质及全固态LFP锂离子电池性能的影响

将Li1.5Al0.5Ge1.5(PO4)3（LAGP）与少量PEO(LiX)复合,采用溶液浇注法制备了以LAGP为主相的固体复合电解质,研究了LiClO4、LiTFSI、LiBOB 3种锂盐对固体复合电解质离子电导率、电化学稳定窗口、与锂负极界面的化学稳定性和电化学稳定性的影响以及锂盐种类对LFP固态电池循环及倍率性能的影响。研究结果表明,采用LiClO4、LiTFSI、LiBOB 3种锂盐制备的固体复合电解质分解电压均超过5 V,具有较好的电化学稳定性。LAGP-PEO(LiTSFI)固体复合电解质的离子电导率以及室温对锂界面的稳定性相对更高。LAGP-PEO (LiBOB)与锂的界面在60 ℃时相对更稳定。与之对应,采用LAGP-PEO(LiTSFI)和LAGP-PEO(LiBOB)固体复合电解质的LFP全固态电池,分别在25 ℃和60 ℃具有最高的比容量和最好的循环稳定性。     

Ash-forming elements in four Scandinavian wood species. Part 1: Summer harvest

Woody biomass in Finland and Sweden comprises mainly four wood species: spruce, pine, birch and aspen. To study the ash, which may cause problems for the combustion device, one tree of each species were cut down and prepared for comparisons with fuel samples. Well-defined samples of wood, bark and foliage were analyzed on 11 ash-forming elements: Si, Al, Fe, Ca, Mg, Mn, Na, K, P, S and Cl. The ash content in the wood tissues (0.2–0.7%) was low compared to the ash content in the bark tissues (1.9–6.4%) and the foliage (2.4–7.7%). The woods’ content of ash-forming elements was consequently low; the highest contents were of Ca (410–1340 ppm) and K (200–1310), followed by Mg (70–290), Mn (15–240) and P (0–350). Present in the wood was also Si (50–190), S (50–200) and Cl (30–110). The bark tissues showed much higher element contents; Ca (4800–19,100 ppm) and K (1600–6400) were the dominating elements, followed by Mg (210–2400), P (210–1200), Mn (110–1100) and S (310–750), but the Cl contents (40–330) were only moderately higher in the bark than in the wood. The young foliage (shoots and deciduous leaves) had the highest K (7100–25,000 ppm), P (1600–5300) and S (1100–2600) contents of all tissues, while the shoots of spruce had the highest Cl contents (820–1360) and its needles the highest Si content (5000–11,300). This paper presented a new approach in fuel characterization: the method excludes the presence of impurities, and focus on different categories of plant tissues. This made it possible to discuss the contents of ash element in a wide spectrum of fuel-types, which are of large importance for the energy production in Finland and Sweden.     

NEXT GENERATION ENGINEERED MATERIALS FOR ULTRA SUPERCRITICAL STEAM TURBINES

正1 ABSTRACT To reduce the effect of global warming on our climate,the levels of CO2emissions should be reduced.One way to do this is to increase the efficiency of electricity production from fossil fuels.This will in turn reduce the amount of CO2emissions for a given power output.Using US practice for efficiency calculations,then a move from a typical US plant running at 37%efficiency to a 760℃/38.5 MPa(1 400/5 580 psi)plant running at 48%efficiency would reduce CO2emissions by 170kg/MW.hr or 25%.     

Contents in Volume 23,2014

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Aerodynamic performance effects of leading-edge geometry in gas-turbine blades

The purpose of this paper is to illustrate the advantages of the direct surface-curvature distribution blade-design method, originally proposed by Korakianitis, for the leading-edge design of turbine blades, and by extension for other types of airfoil shapes. The leading edge shape is critical in the blade design process, and it is quite difficult to completely control with inverse, semi-inverse or other direct-design methods. The blade-design method is briefly reviewed, and then the effort is concentrated on smoothly blending the leading edge shape (circle or ellipse, etc.) with the main part of the blade surface, in a manner that avoids leading-edge flow-disturbance and flow-separation regions. Specifically in the leading edge region we return to the second-order (parabolic) construction line coupled with a revised smoothing equation between the leading-edge shape and the main part of the blade. The Hodson–Dominy blade has been used as an example to show the ability of this blade-design method to remove leading-edge separation bubbles in gas turbine blades and other airfoil shapes that have very sharp changes in curvature near the leading edge. An additional gas turbine blade example has been used to illustrate the ability of this method to design leading edge shapes that avoid leading-edge separation bubbles at off-design conditions. This gas turbine blade example has inlet flow angle 0°, outlet flow angle −64.3°, and tangential lift coefficient 1.045, in a region of parameters where the leading edge shape is critical for the overall blade performance. Computed results at incidences of −10°,   −5°,   +5°,   +10° are used to illustrate the complete removal of leading edge flow-disturbance regions, thus minimizing the possibility of leading-edge separation bubbles, while concurrently minimizing the stagnation pressure drop from inlet to outlet. These results using two difficult example cases of leading edge geometries illustrate the superiority and utility of this blade-design method when compared with other direct or inverse blade-design methods.     

Hydrogen production by steam-gasification of carbonaceous materials using concentrated solar energy – V. Reactor modeling,optimization, and scale-up

A chemical reactor for the steam-gasification of carbonaceous particles (e.g. coal, coke) is considered for using concentrated solar radiation as the energy source of high-temperature process heat. A two-phase reactor model that couples radiative, convective, and conductive heat transfer to the chemical kinetics is applied to optimize the reactor geometrical configuration and operational parameters (feedstock's initial particle size, feeding rates, and solar power input) for maximum reaction extent and solar-to-chemical energy conversion efficiency of a 5 kW prototype reactor and its scale-up to 300 kW. For the 300 kW reactor, complete reaction extent is predicted for an initial feedstock particle size up to 35 μm at residence times of less than 10 s and peak temperatures of 1818 K, yielding high-quality syngas with a calorific content that has been solar-upgraded by 19% over that of the petcoke gasified.     

汽轮机数字电液调节系统挂闸异常的技术完善

分析了200MW汽轮机数字电液调节系统在运行中存在的挂闸异常问题,采取了相应的技术处理措施,且运行实践效果良好。     

新型高压共轨ECU升压模块的数字化开发与优化

为了提高喷油器电磁阀的响应速率,提出了一种基于CPLD(复杂可编程逻辑器件)应用于高压共轨ECU的数字升压模块。鉴于该升压电路结构参数多,其升压电压的恢复响应要求高等特征,基于Pspice建立了升压电路的仿真模型,研究了不同电路参数下升压模块的输出特性,全面优化了该升压模块的性能。结果显示,该升压模块的最大转换效率可以达90%以上。在柴油发动机上对ECU的试验表明,升压电压最大波动不超过10%,其恢复时间仅为1.3ms,功率管最大温升仅为41℃,满足整机运行范围内ECU的需求。     

Trace metal chemistry and silicification of microorganisms in geothermal sinter, Taupo Volcanic Zone, New Zealand

As part of a pilot study investigating the role of microorganisms in the immobilisation of As, Sb, B, Tl and Hg, the inorganic geochemistry of seven different active sinter deposits and their contact fluids were characterised. A comprehensive series of sequential extractions for a suite of trace elements was carried out on siliceous sinter and a mixed silica-carbonate sinter. The extractions showed whether metals were loosely exchangeable or bound to carbonate, oxide, organic or crystalline fractions. Hyperthermophilic microbial communities associated with sinters deposited from high temperature (92–94°C) fluids at a variety of geothermal sources were investigated using SEM. The rapidity and style of silicification of the hyperthermophiles can be correlated with the dissolved silica content of the fluid. Although high concentrations of Hg and Tl were found associated with the organic fraction of the sinters, there was no evidence to suggest that any of the heavy metals were associated preferentially with the hyperthermophiles at the high temperature (92–94°C) ends of the terrestrial thermal spring ecosystems studied.     

Assessment methods of material ageing using Sdobyrev''s creep rupture model

The physical aspects of the activation energy, in higher and high temperatures, of the metal creep process were examined. The research results of creep-rupture in a uniaxial stress state and the criterion of creep-rupture in biaxial stress states, at two temperatures, are then presented. For these studies creep-rupture, taking case iron as an example the energy and pseudoenergy activation was determined. For complex stress states the criterion of creep-rupture was taken to be Sdobyrev's, i.e. σ_red = σ₁ β + (1 − β)σ_i, where: σ₁-maximal principal stress, σ_i-stress intensity, β-material constant (at variable temperature β = β(T)). The methods of assessment of the material ageing grade are given in percentages of ageing of new material in the following mechanical properties: 1) creep strength in uniaxial stress state, 2) activation energy in uniaxial stress state, 3) criterion creep strength in complex stress states, 4) activation pseudoenergy in complex stress states. The methods 1) and 3) are the relatively simplest because they result from experimental investigations only at nominal temperature of the structure work, however, for methods 2) and 4) it is necessary to perform the experimental investigations at least at two temperatures.     

Production of hydrogen from sewage biosolids in a continuously fed bioreactor: Effect of hydraulic retention time and sparging

Hydrogen was produced from primary sewage biosolids via mesophilic anaerobic fermentation in a continuously fed bioreactor. Prior to fermentation the sewage biosolids were heated to 70 °C for 1 h to inactivate methanogens and during fermentation a cellulose degrading enzyme was added to improve substrate availability. Hydraulic retention times (HRT) of 18, 24, 36 and 48 h were evaluated for the duration of hydrogen production. Without sparging a hydraulic retention time of 24 h resulted in the longest period of hydrogen production (3 days), during which a hydrogen yield of 21.9 L H₂ kg⁻¹ VS added to the bioreactor was achieved. Methods of preventing the decline of hydrogen production during continuous fermentation were evaluated. Of the techniques evaluated using nitrogen gas to sparge the bioreactor contents proved to be more effective than flushing just the headspace of the bioreactor. Sparging at 0.06 L L min⁻¹ successfully prevented a decline in hydrogen production and resulted in a yield of 27.0  L H₂ kg⁻¹ VS added, over a period of greater than 12 days or 12 HRT. The use of sparging also delayed the build up of acetic acid in the bioreactor, suggesting that it serves to inhibit homoacetogenesis and thus maintain hydrogen production.