基于分子轨道杂化的高电压钠离子电池层状氧化物正极材料北大核心CSCD

O3型层状过渡金属氧化物NaNi_(0.5)Mn_(0.5)O_(2)是目前最有应用前景的钠离子电池正极材料之一。然而,由于在充放电过程中过渡金属层的滑移,O3型正极材料伴随着多重不可逆的复杂相变,所以其应用受到了限制。另外,O3-NaNi_(0.5)Mn_(0.5)O_(2)正极的容量主要集中在3 V左右的低电压区域,在充放电过程中这一区域很容易发生O3-P3相变,所以限制了其能量密度。本研究提出了一种精准的化学元素取代策略来解决这些问题。通过Sn^(4+)掺杂来抑制过渡金属层的滑移,从而抑制循环过程中的不可逆相转变。同时,由于Sn^(4+)具有独特的外层电子结构,在d轨道上没有单电子,无法与O 2p轨道发生杂化,所以O 2p轨道就只与Ni eg轨道发生杂化,增大了Ni—O键的离子度,提高了Ni的氧化还原电势。因此,NaNi_(0.5)Sn_(0.5)O_(2)正极材料的中值电压高达3.28 V。同时,该电极材料表现出较为优异的电化学性能和动力学性质。本工作基于分子轨道杂化对O3型正极材料的氧化还原电势实现了可控调制,从而获得了具有高电压的钠离子电池层状氧化物正极材料。     

自由基簇射降解甲苯和二甲苯的量子化学研究

采用密度泛函法（DFT）,同时考虑典型的异构,对甲苯、二甲苯中的C—C,C—H键解离能进行计算,计算结果与实验值较好地吻合。分析对比了各解离能的大小,发现甲基上的C—H键解离能最小,苯环侧链上的C—C键解离能稍大。其他C—H键解离能最大。从而指出了甲苯二甲基取代苯中键解离能大小的一般规律,预测了自由基解离甲、苯二甲苯的通道及其解离所需要的能量。结合蒙特卡罗模拟出的气隙空间电子平均能量分布,指出了断裂特定共价键所需输入的电压值。     

一种无电压尖峰的改进型分裂Δ源逆变器

针对传统Δ源逆变器(Δ-source inverter,DSI)存在着开关管有较大的电压尖峰、高增益下输出电能质量差的问题,在分裂Δ源逆变器(Split Δ-source inverter,SDSI)的基础上,加入电压箝位单元,提出了一种改进型分裂Δ源逆变器(Improved split Δ-source inverter,ISDSI),研究了它的拓扑结构与工作状态,重点分析了其稳态升压特性与消除电压尖峰过程,并计算了各开关器件的电压应力。新提出的拓扑保留了SDSI升压占空比和调制因数同向调整的优点,这有助于改善高增益下输出电能质量。此外,新拓扑消除了开关管电压尖峰,降低了开关管和二极管的电压应力。Matlab/Simulink软件仿真和样机试验的结果验证了变换器的性能,证明了所提逆变器能够有效解决Δ源逆变器存在的突出问题。     

全钒液流电池在充电结束搁置阶段的开路电压变化

本工作通过对全钒液流电池的充电-搁置实验,对电池搁置阶段的开路电压变化进行探索。实验发现,全钒液流电池的开路电压变化与非液流储能电池有所不同,主要由跃降、缓慢下降、缓慢上升和趋于稳定四个过程组成。本工作首先对全钒液流电池开路电压的四个过程逐步进行分析,然后重点针对开路电压出现缓慢上升的原因及影响因素进行探索。实验结果表明全钒液流电池开路电压缓慢上升的过程与电池内电解液体积占比和流量有关,是全钒液流电池在充电结束搁置阶段的重要特征。电池内电解液体积占比越小,开路电压缓慢上升过程越长,上升幅度越小。电解液流量越大,开路电压缓慢上升过程越短,上升幅度越小。     

基于差分电压和Elman神经网络的锂离子电池RUL预测方法

锂离子电池剩余使用寿命(remaining useful life,RUL)预测对电池的使用维护极为重要,提出一种基于差分电压和Elman神经网络预测锂离子电池RUL的方法.首先,根据美国国家航天航空局(National Aeronautics and Space Administration,NASA)的锂离子电池数据集,分析电池差分电压曲线和充放电曲线,提取电池容量退化特征量;其次,通过Pearson法分析特征量之间的相关性,将充电差分电压曲线初始拐点值、放电差分电压曲线峰值、放电时间、静置时间作为电池RUL预测的间接健康因子;最后,建立以上述间接健康因子为输入,电池容量为输出的Elman神经网络,进行锂离子电池的RUL预测.基于不同间接健康因子和不同神经网络的四种电池容量预测对比实验表明,在间接健康因子中加入充电差分电压曲线初始拐点值和放电差分电压曲线峰值可以提高电池寿命预测精度,Elman神经网络可准确预测电池容量.基于不同循环次数预测电池RUL,预测的平均均方根误差为1.55％.     

MOFs及其衍生物在锂-氧气电池正极中的研究进展

金属有机骨架材料(MOFs)及其衍生物因其灵活多变的化学组成和多孔结构等独特优点而成为锂-氧气(Li-O₂)电池正极的候选催化剂。本文通过对近期相关文献的分析,综述了MOFs基催化剂的设计和合成策略,重点介绍了MOFs热解衍生碳基材料、MOFs衍生单原子催化剂以及原始MOFs材料在Li-O₂电池中的应用,分析了MOFs及其衍生物对ORR/OER的催化机理。综合分析表明,构建具有高密度催化活性位点、结构稳定、孔隙率高、导电性良好的MOFs材料及其衍生物是今后开发高效Li-O₂电池正极催化剂的发展方向。     

锂离子电池正极材料循环稳定性的基因规律

锂离子电池正极材料需要有较大的能量密度和稳定的循环寿命,循环寿命与其脱锂前后的结构变化有直接关系.但是,影响循环寿命的原子层次因素是什么,还没有明确的答案.探究和优化正极材料的核心工作就是要寻找微观结构与性能之间的关系,这里不仅需要用到大数据统计,也需要对比分析脱锂前后的结构变化特征参数.通过分子动力学方法计算得到了1...     

基于安全电压的双馈风电机组高电压穿越判别方法

基于双馈风电机组的动态无功支持能力,在电网电压骤升时协调控制网侧变流器和发电机定子输出的无功功率,维持直流侧母线电压的安全稳定运行。根据DFIG直流侧电容的高电压穿越安全要求,定义了电网电压骤升时双馈风力发电机组接入电压的安全电压。然后基于安全电压给出了DFIG在电网电压骤升时能否实现高电压穿越的判断依据,并给出了其高电压穿越时的无功协调输出策略。仿真结果验证了所提的方法。     

Progress on high energy density lithium batteries by CAS battery research group

提高动力电池的能量密度将显著延长续航里程,对发展电动汽车具有重要的意义.中国科学院在2013年底部署了中国科学院战略性先导科技专项,通过合作研究,积极探索了第三代锂离子电池,固态锂电池,锂-硫电池和锂-空气电池等电池体系.其中,采用纳米硅碳负极,富锂正极的24 A·h的锂离子电池单体,质量能量密度达到374 W·h/kg,体积能量密度达到577 W·h/L.8 A·h固态聚合物锂电池60 ℃下能量密度达到240 W·h/kg,基于无机陶瓷固态电解质的固态锂电池室温下能量密度达到240 W·h/kg.37 A·h的锂硫电池单体室温能量密度达到566 W·h/kg,50 ℃达到616 W·h/kg.5 A·h锂空气电池单体能量密度达到526 W·h/kg.目前这些样品电池在综合技术指标方面离实际应用还有较大的距离,需要进一步深入细致的进行基础科学与关键技术方面的研究.从长远考虑,电池能量密度的提高必然进一步增加电池安全性风险,因此不同形式的固态锂电池将是未来长续航动力锂电池的发展方向.     

Fundamental scientific aspects of lithium ion batteries(ⅩⅣ)—Calculation methods

基础理论的创新与计算机性能的大幅度提升为高精度与多尺度的计算模拟提供了可能,这些方法也在锂离子电池的研究中得到了广泛的应用。本文介绍了第一性原理、密度泛函理论、分子动力学、蒙特卡罗、相场模拟、分子力场、有限元等不同时间与空间尺度上的模拟方法的基本原理,并探讨了这些方法在锂离子电池基础研究中的应用,如计算电池电压、电极材料的电子结构、能带结构、迁移路径、缺陷生成能、离子在材料体相及不同微观结构中的输运、材料中温度场分布、应力场分布等。     

汽车空调制冷剂直冷动力电池热管理系统的PID控制研究

电池热管理对电动汽车的安全和寿命至关重要。本文采用铝翅片铜管作为基础结构,设计一种结构紧凑、轻量型的18650型锂离子电池模组,采用基于PID原理的算法作为电动汽车空调系统电子膨胀阀的控制方案,实验研究R134a制冷剂直接气液两相流冷却电池模组的换热性能。结果表明：所提出的电池热管理系统能够快速响应温度的变化,并降低电池模组的温度。此外,当控制方案为动态温度PID算法时,电池模组以1 C倍率放电过程中电池之间的最大温差小于4℃,并且电池模组的最高温度低于36℃。     

First Principles Peierls-Boltzmann Phonon Thermal Transport: A Topical Review

The advent of coupled thermal transport calculations with interatomic forces derived from density functional theory has ushered in a new era of fundamental microscopic insight into lattice thermal conductivity. Subsequently, significant new understanding of phonon transport behavior has been developed with these methods, and because they are parameter free and successfully benchmarked against a variety of systems, they also provide reliable predictions of thermal transport in systems for which little is known. This topical review will describe the foundation from which first principles Peierls-Boltzmann transport equation methods have been developed and briefly describe important necessary ingredients for accurate calculations. Sample highlights of reported work will be presented to illustrate the capabilities and challenges of these techniques and to demonstrate the suite of tools available, with an emphasis on thermal transport in micro- and nanoscale systems. Finally, future challenges and opportunities will be discussed, drawing attention to prospects for methods development and applications.     

木糖热解过程中丙酮形成机理的理论研究

丙酮是半纤维素热解过程中重要的酮类产物,但其生成机理仍不清楚。本文以典型的半纤维素基单糖——木糖为模型化合物,基于密度泛函理论方法计算其分解生成丙酮的可能路径,同时讨论了温度对丙酮形成路径竞争性的影响。结果表明,木糖热解过程中,四碳中间体3-羰基丁醛是形成丙酮的重要中间体。木糖热解最可能经3-戊酮糖分解路径形成C1-C2-C3位或C3-C4-C5位丙酮,同时也易经D-木糖分解路径形成C3-C4-C5位丙酮,高温下木糖热解生成C2-C3-C4位丙酮的比例增多。     

Higher fullerenes as electron acceptors for polymer solar cells: A quantum chemical study

In the present study, we have used quantum chemical methods to study the energy levels of the frontier orbitals of higher fullerene derivatives (from C₇₀ to C₈₄ and having the same addend as in [6,6]-phenyl C₆₁-butyric acid methyl ester) with the aim to understand if they can be used as electron acceptors in bulk heterojunction polymer–fullerene solar cells. Higher fullerenes have a stronger and broader absorption compared to C₆₀ and they can improve the current output of the corresponding devices. The geometries of all the compounds were optimized with the density functional theory at the B3LYP/3-21G* level of calculation. The lowest unoccupied molecular orbital (LUMO) levels of the investigated compounds correlate well with the reduction potentials (obtained by cyclic voltammetry) of the already prepared species. We found that the LUMO level depends not only on the fullerene size (number of carbons of the cage) and constitutional isomer, but also on the position and, in some cases, the addend orientation. This issue should be considered because for a proper device operation, a well-defined LUMO is required. The position of the LUMO level of some higher fullerene derivatives can be suitable for low-bandgap polymers.     

Nickel cobalt oxide nanowires-modified hollow carbon tubular bundles for high-performance sodium-ion hybrid capacitors

Sodium-ion hybrid capacitors are a prospective energy storage device candidate that couples the superiorities of battery-type and capacitive storage mechanisms. In this study, we fabricate a composite of NiCo₂O₄ nanowires with carbon tubular bundles (CTBs) via a facile hydrothermal and annealing procedure. The density functional theory (DFT) calculations are performed to evaluate the bonding strength between the two components of the composite, the binding energy of the NiCo₂O₄ is calculated to be −0.952 J m⁻², indicating that the NiCo₂O₄ nanowires can be stabilized on both sides of the carbon tubular bundles, which leads to a good cycling performance. Moreover, the composite in this work exhibits a metallic property because of the introduction of carbon material. As expected, when used for sodium storage, the NiCo₂O₄/CTBs shows a high capacity of 298 mA h g⁻¹ at 1 A g⁻¹ and high capacity retention of 92% after 500 cycles, which are superior than the bare NiCo₂O₄ electrode. Consequently, the sodium-ion hybrid capacitor is also assembled with NiCo₂O₄/carbon tubular bundles and commercial activated carbon, which achieves high energy density of 99 Wh kg⁻¹ in a wide potential range from 0.5 V to 4.0 V.     

Dehydrogenation of a liquid organic hydrogen carrier compound 1-(3-cyclohexylpropyl)-3-ethylcyclohexane: A density functional theory study

As a compound for liquid organic hydrogen carrier (LOHC) applications, 1-(3-cyclohexylpropyl)-3-ethylcyclohexane was designed and its dehydrogenation reaction was investigated using density functional theory calculations. To check how this compound could be stable, vibrational frequency analysis and formation energy calculations were conducted. Our findings revealed that this LOHC compound was dynamically and chemically stable. Using Mulliken population analysis, the dehydrogenation process was clearly explained. To reduce the dehydrogenation energy, different substituents, such as N, Cl, and Br were used. Our results suggested that N-substitution could be potentially suitable to lower the dehydrogenation energy. Reaction barriers of pristine and N-substituted systems for dehydrogenation reactions were investigated through nudged elastic band methods. In addition, the gap between HOMO and LUMO was calculated to check chemical reactivity.     

一种基于三端口能量路由的单级式光储并网系统及其高压穿越技术

该文提出一种具有高压穿越能力的基于三端口能量路由的单级式光储并网系统（PV-ESS）。光伏最大功率跟踪始终由三相变换器控制完成。多端口能量路由器可根据不同运行工况使储能灵活接入,平抑光伏输出,使得系统具有更高的效率。在电网高压故障下,通过储能装置抬升直流母线电压,从而使系统具有高压穿越的能力,可在电网高压状态下不脱网连续运行,直至故障恢复。