Thermal transport in lithium-ion battery: A micro perspective for thermal management

In recent years, lithium ion (Li-ion) batteries have served as significant power sources in portable electronic devices and electric vehicles because of their high energy density and rate capability. There are growing concerns towards the safety of Li-ion batteries, in which thermal conductivities of anodes, cathodes, electrolytes and separator play key roles for determining the thermal energy transport in Li-ion battery. In this review, we summarize the state-of-the-art studies on the thermal conductivities of commonly used anodes, cathodes, electrolytes and separator in Li-ion batteries, including both theoretical and experimental reports. First, the thermal conductivities of anodes and cathodes are discussed, and the effects of delithiation degree and temperature of materials are also discussed. Then, we review the thermal conductivities of commonly used electrolytes, especially on solid electrolytes. Finally, the basic concept of interfacial thermal conductance and simulation methods are presented, as well as the interfacial thermal conductance between separator and cathodes. This perspective review would provide atomic perspective knowledge to understand thermal transport in Li-ion battery, which will be beneficial to the thermal management and temperature control in electrochemical energy storage devices.     

一代材料，一代电池：正极材料研究推动锂离子动力电池的升级换代

一代材料,一代电池。锂离子电池正极材料的研究不断推动着动力电池的升级换代。第一代动力电池的正极材料为锰酸锂LiMn₂O₄,其低温性能好、成本低和安全性高,但电池能量密度不够高。第二代动力电池正极材料为磷酸铁锂LiFePO₄和三元正极材料镍钴锰NCM/镍钴铝NCA。磷酸铁锂正极材料的优势是长寿命、低成本、高安全性。三元锂正极材料的特点是大容量、高能量密度、快充效率高。第三代动力电池的正极材料是高电压镍锰酸锂LiNi_0.5Mn_1.5O₄和镍酸锂LiNiO₂,主要解决第二代面临的低成本和长续航不能兼顾的问题以及更长里程问题。文章首先回顾第一、二代的锰酸锂、磷酸铁锂和三元正极材料的研究历程、优缺点及发展近况,之后介绍和展望下一代高电压镍锰酸锂和镍酸锂正极材料。     

LiVPO4F: A new active material for safe lithium-ion batteries

In this paper, we report the latest findings for the new lithium vanadium fluorophosphate cathode material, LiVPO₄F. High quality samples have been prepared using a carbothermal reduction approach and extensive electrochemical and DSC measurements have been performed. In graphite based lithium-ion cells, the LiVPO₄F demonstrates reversible specific capacity behavior approaching theoretical. The lithium-ion system operates with an average discharge voltage around 4 V, low polarization and with good rate capability. These results indicate that the active material possesses exemplary electrochemical performance and may well be suitable as a replacement for LiCoO₂ in commercial lithium-ion cells. DSC measurements on charged cathodes indicate the thermal stability behavior expected for a phosphate based active material.     

A review on microwave synthesis of electrode materials for lithium-ion batteries

The applications of microwave processing of electrode materials for Li-ion batteries have been reviewed. This paper intends to insist at the advantages of the microwave processing and its credentials for commercialization. In order to achieve successive commercialization/industrial application, a systematic understanding of the microwave processing becomes imperative. In the advent of this, an extensive study on the behavior of material in electromagnetic field has been presented. Microwave processing of various materials like lithium cobalt oxide, lithium manganese oxide, lithium nickel oxide, lithium titanium oxide and their derivatives, copper bismuth oxide, antimony sulfide, and tin oxide graphite has been reviewed in detail. Also, the dependence of microwave processing in operating frequency, geometry, preheating, soaking time, susceptor material, and single (or) multimode cavity has been reviewed.     

反应堆的大规模几何分层建模

工程上大型设备使用CSG建模时需要数量极大的三维体素, 例如组成大亚湾堆芯模型的体素就有数十万个。JLAMT是北京应用物理与计算数学研究所面向蒙特卡洛核子输运计算开发的大规模并行可视建模工具软件,本文面向粒子输运程序的自动、可视化建模,开发了分层建模管理模块,实现分层建模并管理图层,从而简化建模和参数设置的操作。模块还增加快速查找、属性批量编辑和局部检查等功能,提高面向蒙特卡洛核子输运计算的三维复杂模型的建模效率。     

反应堆的大规模几何分层建模

工程上大型设备使用CSG建模时需要数量极大的三维体素, 例如组成大亚湾堆芯模型的体素就有数十万个。JLAMT是北京应用物理与计算数学研究所面向蒙特卡洛核子输运计算开发的大规模并行可视建模工具软件,本文面向粒子输运程序的自动、可视化建模,开发了分层建模管理模块,实现分层建模并管理图层,从而简化建模和参数设置的操作。模块还增加快速查找、属性批量编辑和局部检查等功能,提高面向蒙特卡洛核子输运计算的三维复杂模型的建模效率。     

Surface modifications of electrode materials for lithium-ion batteries: status and trends

The research on the electrodes of Li-ion batteries aims to increase the energy density and the power density, improve the calendar and the cycling life, without sacrificing the safety issues. A constant progress through the years has been obtained owing to the surface treatment of the particles, in particular the coating of the particles with a layer that protects the core region from side reactions with the electrolyte, prevents the loss of oxygen, and the dissolution of the metal ions in the electrolyte, or simply improve the conductivity of the powder. The purpose of the present work is to review the different surface modifications that have been tried in the past for the different electrodes that are currently commercialized, or considered as promising, including the three families of positive electrodes (lamellar, spinel, and olivine families) and the three negative electrodes (carbon, Li₄Ti₅O₁₂, and silicon). The role of the different coats used to improve either the surface conductivity, or the thermal stability, or the structural integrity is discussed. The limits in the efficiency of these different coats are also analyzed along with the understanding of the surface modifications that have been proposed.     

A review of research on hematite as anode material for lithium-ion batteries

Hematite (α-Fe₂O₃) nanomaterials have been investigated intensively as a promising anode material for Li-ion batteries due to their advantages such as high theoretical capacity, low cost, environmental friendliness, high resistance to corrosion, etc. However, their practical application is hampered by poor capacity retention, low Coulombic efficiency, and poor high-rate capacity. To overcome these drawbacks, many effective works have been proposed. This review focuses first on the present status of α-Fe₂O₃ nanomaterials in the field of Li-ion batteries including their features, synthesized methods, modification, application and then on their near future development.     

Shape-controlled porous carbon from calcium citrate precursor and their intriguing application in lithium-ion batteries

Porous carbon nanosheets (PCNSs), porous carbon nanofibers (PCNFs), and flowerlike porous carbon microspheres (FPCMs) were successfully synthesized through a carbonization method combined with a simple acid pickling treatment using calcium citrate as the precursor. The as-prepared products show uniform morphologies, in which the FPCMs are self-assembled from PCNSs. As anodes of lithium-ion (Li-ion) batteries, these carbon materials deliver a stable reversible capacity above 515 mAh g^?1 after 50 cycles at 100 mA g^?1. Compared with PCNSs and PCNFs, FPCMs demonstrate preferable rate capability (378 mAh g^?1 at 1 A g^?1) and cyclability (643 mAh g^?1 at 100 mA g^?1). These results suggest that an appropriate select of morphology and structure will significantly improve the lithium storage capacity. The study also indicates that the novel shape-controlled porous carbon materials have potential applications as electrode materials in electronic devices.     

Synthesis,characterization, and electrochemical properties of lithium-based fluorosulfate nanoparticles as cathode for lithium-ion batteries

Lithium-based fluorosulfate nanoparticles were synthesized by a simple and fast solid state reaction from the precursors FeSO₄?7H₂O and LiF ground by high energy ball milling. Through the introduction of excess of LiF, relatively pure LiFeSO₄F phase with polycrystalline structure was obtained. The structure, morphology, and element valence state were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectra (XPS). The results demonstrate uniformly distributed particles and larger particles consisted of single crystalline structure, besides the valence states for different elements were analyzed and Fe²⁺ was confirmed. The cyclic voltammograms (CV) and charge-discharge cycling performances were employed to characterize electrochemical properties of prepared cathode material. It is very interesting that double redox peaks appeared reversibly. Meanwhile, it exhibited a relatively higher first-discharge capacity of 115 mAh/g at 0.05C and it still maintained above 60 mAh/g capacity after experiencing 30 times cycles at final 2C rate.     

Physics towards next generation Li secondary batteries materials: A short review from computational materials design perspective

The physics that associated with the performance of lithium secondary batteries (LSB) are reviewed. The key physical problems in LSB include the electronic conduction mechanism, kinetics and thermodynamics of lithium ion migration, electrode/ electrolyte surface/interface, structural (phase) and thermodynamics stability of the electrode materials, physics of intercalation and deintercalation. The relationship between the physical/chemical nature of the LSB materials and the batteries performance is summarized and discussed. A general thread of computational materials design for LSB materials is emphasized concerning all the discussed physics problems. In order to fasten the progress of the new materials discovery and design for the next generation LSB, the Materials Genome Initiative (MGI) for LSB materials is a promising strategy and the related requirements are highlighted.     

Raman spectroscopic and structural studies of heat-treated graphites for lithium-ion batteries

Standard graphite TIMREX® SLX 50 was oxidised at 500–800 °C under air atmosphere in a muffle and a rotary furnace. Scanning Electron Microscopy (SEM), Raman spectroscopy, and X-Ray Powder Diffraction (XRD) were used to study the changes in surface morphology and crystallinity. The results show a slight increase of the L_a value and a decrease of the rhombohedral fraction with increased heat-treatment temperature (HTT). XRD measurements show no significant change in L_a values within the bulk of graphite samples. Above 700 °C SEM images of graphite reveals holes and cavities, whereas heat-treatment temperatures below 700 °C do not significantly affect graphite materials parameters.     

Preparation of carbon nanoparticles from electrolysis of molten carbonates and use as anode materials in lithium-ion batteries

The electrochemical reduction of molten Li–Na–K carbonates at 450 °C provides “quasi-spherical” carbon nanoparticles with size comprised between 40 and 80 nm (deduced from AFM measurements). XRD analyses performed after washing and heat-treatment at various temperatures have revealed the presence of graphitised and amorphous phases. The d₀₀₂ values were close to the ideal one obtained for pure graphite. Raman spectroscopy has pointed out surface disordering which increases with increasing temperature of the heat-treatment. The presence of Na and Li on the surface of the carbon powder has been evidenced by SIMS. The maximum Na and Li contents were observed for carbon samples heat-treated at 400 °C. Their electrochemical performances vs. the insertion/deinsertion of lithium cations were studied in 1 M LiPF₆–EC : DEC : DMC (2 : 1 : 2). The first charge–discharge cycle is characterised by a high irreversible capacity as in the case of hard-disordered carbon materials. However, the potential profile in galvanostatic mode is intermediate between that usually observed for graphite and amorphous carbon: rather continuous charge–discharge curves sloping between 1.5 and 0.3 V vs. Li / Li⁺, and successive phase transformations between 0.3 and 0.02 V vs. Li / Li⁺. The best electrochemical performances were obtained with carbon powders heat-treated at 400 °C which exhibits a reversible capacity value of 1080 mAh g^− 1 (composition of Li_2.9C₆). This sample has also both the lowest surface disordering (deduced from Raman spectroscopy), and the highest Na and Li surface contents (deduced from SIMS).     

Defect silicene and graphene as applied to the anode of lithium-ion batteries: Numerical experiment

Mechanical properties and stability of two layers of defect silicene supported by graphene sheets, between which the lithium ion passes under an electrostatic field, are studied by the molecular dynamics method. Defects are mono-, di-, tri-, and hexavacansies. Graphene and silicene edges are rigidly fixed. Graphene sheets contacting with silicene take a convex shape, deflecting outward. Mono- and divacancies in silicene tend to a size decrease; larger vacancies exhibit better stability. The ion motion control using an electric field becomes possible only using perfect silicene or silicene with mono- and divacancies. The ion penetrated through larger defects, and its motion in the silicene channel becomes uncontrolled. When the ion moves in the channel, the most strong stress spikes appear in silicene containing monovacancies. In the case of fixed edges, perfect silicene intercalated with a lithium ion is inclined to accumulate larger stresses than silicene containing defects.     

Synthesis and characterization of mixed vanadium oxide cathode materials for lithium-ion batteries

A family of mixed vanadium oxides LiCo_yNi_(1−y)VO₄ (x=0.2, 0.5 and 0.8) of potential use as high voltage cathode materials in lithium batteries, has been synthesized and characterized. In general the x-ray diffraction analysis showed that these compounds have an inverse spinel structure where about 85 % of the Ni²⁺ and Co²⁺ ions occupies octahedral sites and the rest tetrahedral sites along with the V⁵⁺ ions. Moreover, the annealing temperature plays a key role in determining the particle size, as demonstrated by scanning electron microscope analysis. Cycling voltammetry tests showed that the lithium insertion-extraction process in the LiCo_yNi_(1−y)VO₄ electrode materials occurs reversibly at around 4.3–4.4 V vs. Li and these results are confirmed by cycling tests. The cycling capacity is modest; however the trend of the cycling curves leads to foresee that an increase in capacity may be obtained by extending the charging process beyond 4.6 V vs. Li, once a stable electrolyte will be available. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

大功率锂离子电池储能电源系统的研制与应用

采用高功率高安全性的磷酸铁锂电芯作为储能元件,研制了一种在车载平台中应用的大功率储能电源。在储能电源中配置了高性能的电池采样和主动均衡模块,以及充放电管理系统,可以有效地提高系统可靠性和使用寿命。研制过程中,大功率储能电源进行了大量的工程化试验考核,包括运输安全性、环境适应性、维修性和任务可靠性等工程化指标。最后,21台储能电源在超过55 ℃的高温地区考核超过12个月,储能电源系统的可靠性得到验证。     

Physics of electron and lithium-ion transport in electrode materials for Li-ion batteries

The physics of ionic and electrical conduction at electrode materials of lithium-ion batteries(LIBs) are briefly summarized here, besides, we review the current research on ionic and electrical conduction in electrode material incorporating experimental and simulation studies. Commercial LIBs have been widely used in portable electronic devices and are now developed for large-scale applications in hybrid electric vehicles(HEV) and stationary distributed power stations. However,due to the physical limits of the materials, the overall performance of today's LIBs does not meet all the requirements for future applications, and the transport problem has been one of the main barriers to further improvement. The electron and Li-ion transport behaviors are important in determining the rate capacity of LIBs.     

多层多孔锂离子电池结构的导波频散特征及其应用EI北大核心CSCD

采用状态矩阵与勒让德级数联合法,同步联立Biot理论,构建多层多孔锂离子电池声传播特性理论模型,以厚1.9 mm软包钴酸锂电池为例,数值分析了荷电状态(State of Charge,SOC)对多模态频散曲线的影响规律。同时,建立了电池中的声传播特性频域仿真模型,提取频域仿真中的超声导波频散曲线。此外,以体积小、柔性强的压电纤维复合材料(Macro Fiber Composite,MFC)为基础,实验探究了不同SOC对锂离子电池中声学行为的影响。采用互相关分析获取电池放电过程中声波渡越时间的偏移规律,建立了1.9 mm软包钴酸锂电池的声学波动行为与电池SOC间的映射关系。     

一种求解锂离子电池单粒子模型液相扩散方程的新方法

电解液中的锂离子浓度表达是锂离子电池电化学模型求解的基本任务之一.为了平衡单粒子模型的液相动态性能和计算效率,假设反应仅发生在集电极和电解质界面上,为此,提出一种基于液相扩散方程无穷级数解析解的界面浓度求解新方法.在恒流工况下,利用数列单调收敛准则将解析解转化为一个收敛和函数.在动态工况下,将该解析解简化为输入与和函数的无限离散卷积.利用和函数随时间单调衰减并收敛至零的特性对其进行截断,从而得到有限离散卷积求解算法.对比专业有限元分析软件,该方法在恒流工况和动态工况下均能以较少的计算时间获得相当好的精度.而且,该方法仅有一个配置参数.因此,所提方法将有效减小应用于实时电池管理系统上的电化学模型计算负担.