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.     

Li-ion batteries: Phase transition

Progress in the research on phase transitions during Li+extraction/insertion processes in typical battery materials is summarized as examples to illustrate the significance of understanding phase transition phenomena in Li-ion batteries.Physical phenomena such as phase transitions(and resultant phase diagrams) are often observed in Li-ion battery research and already play an important role in promoting Li-ion battery technology. For example, the phase transitions during Li+insertion/extraction are highly relevant to the thermodynamics and kinetics of Li-ion batteries, and even physical characteristics such as specific energy, power density, volume variation, and safety-related properties.     

Review of 5-V electrodes for Li-ion batteries: status and trends

Lithium-ion batteries have dominated the battery industry for the past several years in portable electronic devices due to their high volumetric and gravimetric energy densities. The success of these batteries in small-scale applications translates to large-scale applications, with an important impact in the future of the environment by improving energy efficiency and reduction of pollution. We present the progress that allows several lithium-intercalation compounds to become the active cathode element of a new generation of Li-ion batteries, namely the 5-V cathodes, which are promising to improve the technology of energy storage and electric transportation, and address the replacement of gasoline engine by meeting the increasing demand for green energy power sources. The compounds considered here include spinel LiNi_0.5Mn_1.5O₄ and its related doped-structures, olivine LiCoPO₄, inverse spinel LiNiVO₄ and fluorophosphate Li₂CoPO₄F. LiNi_0.5Mn_1.5O₄ thin films, nanoscale prepared materials and surface-modified cathode particles are also considered. Emphasis is placed on the quality control that is needed to guarantee the reliability and the optimum electrochemical performance of these materials as the active cathode element of Li-ion batteries. The route to increase the performance of Li-ion batteries with the other members of the family is also discussed.     

锂离子电池相关材料的Raman光谱学研究

锂离子电池是目前综合性能最好的可充电池。本文总结我们实验室用Raman光谱学研究锂离子电池相关材料的一些结果 ,包括聚合物电解质的微结构和离子输运机制 ,低温热解碳负极材料的结构表征和锂离子在其中的嵌入 /脱出机理 ,元素替代引起正极材料LiMn2 O4的结构变化以及在充放电过程中电极 /电解质界面形成的钝化层的性质及其对电池性能的影响     

中国先进研究堆中子科学平台发展现状及展望

依托中国先进研究堆(CARR)高通量中子源,建成了初具规模的中子科学平台,具备中子散射、中子成像和中子活化分析等多种研究技术。其中,中子散射技术包括中子衍射、小角中子散射及中子反射、非弹性中子散射,可以用于分析材料微观结构和动力学性质;热中子成像和冷中子成像可以用于材料内部缺陷等无损检测;中子活化分析系统可以用于物质内核素成分分析。目前已建成和在建中子谱仪共计19台,并初步配备了样品环境装置,为相关应用研究提供了条件基础,可为我国物理、化学、材料科学、生命科学、能源和环境等领域基础研究及工业应用提供重要技术支撑。CARR中子科学平台始终坚持合作共享对外开放的宗旨,将继续为国内外用户提供优质中子技术,服务基础科学前沿和国家重大创新需求研究。     

锂电池发展简史

由于具有很高的能量密度，锂金属在1958年被引入电池领域，1970年进入锂一次电池的商业研发阶段。自1990年以来，随着正极材料、负极材料与电解质的革新，可充放二次锂电池不断发展并实现商品化。如今锂电池技术仍在继续发展并将进一步改善人类生活。文章对40多年来锂电池技术发展历程进行了简单的回顾。     

Carbon Nanostructures in Lithium Ion Batteries: Past,Present, and Future

Advent of nanotechnology has generated huge interest in application of carbon-based nanomaterials as a possible replacement for conventionally used graphite as anode of Li-ion batteries. Future Li-ion batteries demand high capacity, energy, power, and better safety, while graphite falls short of fulfilling all these necessities. Inspired by high conductivity, flexibility, surface area, and Li-ion insertion ability, a number of nano carbon materials, individually or as a composite, have been studied in detail to identify the best suitable material for next-generation energy storage devices. Many of these nano-C-based structures hold good promise, although issues like density of nanomaterials and scalability are yet to be addressed with confidence. This article aims to summarize the major research directions of nano-C materials in anodic application of Li-ion batteries and proposes possible future research directions in this widely studied field.     

Analysis of Li distribution in ultrathin all-solid-state Li-ion battery (ASSLiB) by neutron depth profiling (NDP)

Lithium-ion batteries are promising energy storage technology devices. They possess many advantages, including high energy density, flexible and lightweight construction and considerable durability. The rapid development of nanotechnologies can further improve their capacity, cycle life and safety. In this experiment, Li-ion diffusion in an all-solid lithium-ion battery (ASSLiB) was studied using the Neutron Depth Profiling (NDP) nuclear analytical technique. The thin ASSLiB system was synthesised by RF magnetron sputtering. The experiment showed that NDP is a very efficient experimental tool for direct analysis of Li distribution in Li batteries. It has been found that the depth profile of Li strongly depends on the state of charge of the battery. About one-third of the total number of Li in ASSLiB can move between the electrodes during charging / discharging. It has been also shown, using the multipixel detectors, that the lateral distribution of Li in ASSLiB is not homogeneous. This can mean, for example, that the position of Li is affected by structural defects that may arise due to variation of the volume or stress of the battery during charging or discharging. In the work are presented first results of measurements performed on ASSLiB of a 1?µm thickness.     

A single dual-mode gas sensor for early safety warning of Li-ion batteries: Micro-scale Li dendrite and electrolyte leakage

Li dendrites and electrolyte leakage are common causes of Li-ion battery failure. H₂, generated by Li dendrites, and electrolyte vapors have been regarded as gas markers of the early safety warning of Li-ion batteries. SnO₂-based gas sensors, widely used for a variety of applications, are promising for the early safety detection of Li-ion batteries, which are necessary and urgently required for the development of Li-ion battery systems. However, the traditional SnO₂ sensor, with a single signal, cannot demonstrate intelligent multi-gas recognition. Here, a single dual-mode (direct and alternating current modes) SnO₂ sensor demonstrates clear discrimination of electrolyte vapors and H₂, released in different states of Li-ion batteries, together with principal component analysis (PCA) analysis. This work provides insight into the intelligent technology of single gas sensors.     

The application of quasi-elastic neutron scattering techniques (QENS) in surface diffusion studies

Neutron scattering techniques such as quasi-elastic neutron scattering, QENS, have proven to be well-suited tools for studying structure and dynamics of surface adsorbed molecules. In contrast to many more widely used surface science techniques neutron scattering allows the microscopic characterization of samples under a wide range of thermodynamic conditions, as the samples are not constrained to ultra high vacuum environment. Moreover, neutron scattering allows the separation of coherent and incoherent scattering, giving access to different diffusive mechanisms such as single particle diffusion, mass transport, rotations, or vibrations. In this paper we will review recent progress and the state-of-the-art in neutron scattering experiments on surface adsorbed molecules in the sub-monolayer coverage range with a specific emphasis on studies of carbon and other high surface density substrates. We will also cover recent progress in theoretical modeling, since the usefulness of neutron scattering data on surface dynamics can be strongly enhanced by computational modeling, such as molecular dynamics (MD) simulations and the development of analytical models.     

Materials for Electrodes of Li-Ion Batteries: Issues Related to Stress Development

Presently, rechargeable Li-ion batteries, possessing highest energy densities among all batte-ries, are used in a major fraction of all portable electronic devices. However, for bestowing the Li-ion batteries suitable for such advanced applications, further improvements in the energy densities (Li-capacities) and in the cycle life are essential. In a broader sense, this can be achieved by replacing the presently used electrode materials by materials possessing higher Li-capacities and minimization of the degradation of such materials with electrochemical cycling. It has been realized that the major reason for degradation in battery performance in terms of capacity with cycling is the disintegration/fragmentation of the active electrode materials due to stresses generated during Li-intercalation/de-intercalation in every cycle. Such stresses arise from the reversible volume changes of the active electrode materials during Li-insertion and removal. In quest of higher energy densities, replacement of the presently used graphitic carbon by potentially higher capacity metallic anode materials (like Si, Sn, and Al) is likely to further accrue this stress related disintegration due to ～30 times higher volume changes experienced by such materials. It has also been recently realized that passivating layer formed on the surface of the electrodes also contributes toward the stress development. After briefly introducing the mechanistic aspects of Li-ion batteries, this article focuses on the reasons and consequences associated with stress developments in different electrode materials, highlighting the various strategies, in terms of designing new electrode com-positions or reducing the microstructural scale, that are being presently adopted to address the stress-related issues. Considering that experimental determination of such stresses is essential toward further progress in Li-ion battery research, this article introduces a recently reported technique developed for real-time measurement of such stresses. It finally concludes by raising some critical issues that need to be resolved through further research in this area.     

以碳粉为负极材料制备锂离子电池及电池性能测试

在能量存储技术中,锂离子电池是高能量密度的电化学电源.以碳为负极材料,涂膜制备了负极片,以锂片为正极片制备了CR2016锂离子电池,并对其性能进行了测试,分析了碳粉为锂电负极材料的特性.     

Cruising in ceramics—discovering new structures for all-solid-state batteries—fundamentals,materials, and performances

Energy storage research has drawn much attention recently due to increasing demand for carbon neutral electrical energy from renewable energy sources such as solar, wind, and hydrothermal. Various electrochemical energy storage and conversion technologies are being considered for their integration into smart grid systems, of which batteries seem to play a vital role due to their wide range of energy densities. In this review, we provide the current status and recent advances in solid-state (ceramic) electrolytes based on inorganic compounds for all-solid-state batteries. This paper is specifically focused on the fundamentals, materials, and performances of solid electrolytes in batteries. A wide spectrum of inorganic solid-state electrolytes is presented in terms of their chemical composition, crystal structure, and ion conduction mechanism. Furthermore, the advantages and main issues associated with different types of inorganic solid electrolytes, including β-alumina, NASICON and LISICON-type, perovskites, and garnet-type for all-solid-state batteries are presented. Among these solid electrolytes, Zr and Ta-based Li-stuffed garnets exhibit high Li-ion conductivity, electrochemical stability window (up to 6  V/Li at room temperature), and chemical stability against reaction with molten elemental Li. However, their stability under humidity and carbon dioxide should be improved to decrease the fabrication and operational costs.     

Advanced characterization and calculation methods for rechargeable battery materials in multiple scales

The structure-activity relationship of functional materials is an everlasting and desirable research question for material science researchers,where characterization and calculation tools are the keys to deciphering this intricate relationship.Here,we choose rechargeable battery materials as an example and introduce the most representative advanced characterization and calculation methods in four different scales:real space,energy,momentum space,and time.Current research methods to study battery material structure,energy level transition,dispersion relations of phonons and electrons,and time-resolved evolution are reviewed.From different views,various expression forms of structure and electronic structure are presented to understand the reaction processes and electrochemical mechanisms comprehensively in battery systems.According to the summary of the present battery research,the challenges and perspectives of advanced characterization and calculation techniques for the field of rechargeable batteries are further discussed.     

Size effects in lithium ion batteries

Size-related properties of novel lithium battery materials, arising from kinetics, thermodynamics, and newly discovered lithium storage mechanisms, are reviewed. Complementary experimental and computational investigations of the use of the size effects to modify electrodes and electrolytes for lithium ion batteries are enumerated and discussed together.Size differences in the materials in lithium ion batteries lead to a variety of exciting phenomena. Smaller-particle materials with highly connective interfaces and reduced diffusion paths exhibit higher rate performance than the corresponding bulk materials. The thermodynamics is also changed by the higher surface energy of smaller particles, affecting, for example,secondary surface reactions, lattice parameter, voltage, and the phase transformation mechanism. Newly discovered lithium storage mechanisms that result in superior storage capacity are also briefly highlighted.     

Understanding oxygen reactions in aprotic Li-O_2 batteries

Although significant progress has been made in many aspects of the emerging aprotic Li-O_2 battery system, an indepth understanding of the oxygen reactions is still underway. The oxygen reactions occurring in the positive electrode distinguish Li-O_2 batteries from the conventional Li-ion cells and play a crucial role in the Li-O_2cell's performance(capacity, rate capability, and cycle life). Recent advances in fundamental studies of oxygen reactions in aprotic Li-O_2 batteries are reviewed, including the reaction route, kinetics, morphological evolution of Li_2O_2, and charge transport within Li_2O_2. Prospects are also provided for future fundamental investigations of Li-O_2 chemistry.     

On the conversion of NDP energy spectra into depth concentration profiles for thin-films all-solid-state batteries

A three-step numerical procedure has been developed, which facilitates the conversion of NDP energy spectra into lithium concentration depth profiles for thin-film Li-ion batteries. The procedure is based on Monte Carlo modeling of the energy loss of charged particles (ions) in the solid media, using the publically available SRIM/TRIM software. For the energy-to-depth conversion, the battery stack has been split into finite volume elements. Each finite volume element becomes a source of ions according to the employed nuclear reaction. Ions loos energy when they move across the battery stack towards the detector. The as-obtained simulated spectra have been compared with the experimentally measured spectra. The thicknesses of the battery stack layers were estimated by minimizing the deviation between the simulated and measured spectra. Subsequently, a relation between the average energy of detected ions and the depth of the corresponding finite volume element, yielding a calibration function, was used to relate that particular part of the spectra with the depth of its source. At the final stage, a Bayesian estimator was used to find the distribution of lithium at a particular depth. The developed procedure was applied to a practically relevant case study of Si immobilization in the LPO electrolyte of all-solid-state thin-film batteries. It is shown that the lithium immobilization process in the LPO electrolyte is responsible for the battery degradation process.     

How M?ssbauer spectroscopy can improve Li-ion batteries

In the domain of Li-ion batteries, M?ssbauer spectroscopy is mainly used for the characterization of electrode materials and the analysis of electrochemical reactions. Depending on the properties under investigation, different approaches are often considered, which are based on ex situ, in situ and operando measurements. The specific electrochemical cells and sample preparations used for such measurements are described in this paper. Applications to selected examples of cathode and anode materials are presented in order to show how M?ssbauer spectroscopy, when associated with other techniques, provides essential information to understand the mechanisms and improves the performances of Li-ion batteries.     

基于单粒子模型与偏微分方程的锂离子电池建模与故障监测

锂离子电池内部结构是一种复杂的分布参数系统, 如果为了降低计算难度而使用常微分方程描述锂离子电池, 可能会引入系统误差, 降低系统模型的可信度, 需要使用偏微分方程建立分布参数系统的精确模型. 本文提出了一种基于单粒子模型和抛物型偏微分方程的锂离子电池系统建模与故障监测系统设计方法, 当锂离子浓度实测值与理想值的残差大于预设门槛时判定分布参数系统处于故障状态. 通过一个仿真实例进行了锂离子电池系统建模和故障诊断实验, 实验证明基于单粒子模型和偏微分方程的锂离子电池故障监测系统具有更高的精确度和可信度.     

用中子散射法研究凝聚态物质的新进展

在近２０年间,由于中子源和散射装置的改进,中子散射在凝聚态物质中的应用日益广泛,许多方面是其它（ｘ射线、电子）散射技术无可比拟的。本文在简单评述供散射用的中子源和散射实验技术进展之后,重点介绍中子散射在凝聚态物质研究中的应用。它们包括晶体结构和磁结构的测定、表面、界面和薄膜的表征、测定结构涨落、磁涨落的现代相变研究、畸变、无序系统（包括分形和小角散射）和高分子材料、高Ｔ＿ｃ氧化物超导体的研究,工业上应用也作了简短讨论。