Modeling the Electrical Conductive Paths within All-Solid-State Battery Electrodes

All-solid-state batteries constitute a very promising energy storage device. Two very important properties of these battery cells are the ionic and the electrical conductivity, which describe the ion and the electron transport through the electrodes, respectively. In this work, a numerical method is presented to model the electrical conductivity, considering the outcome of discrete-element method simulations and the intrinsic conductivities of both the active material particles and the conductive additive particles. The results are calibrated and validated with the help of experimental data of real manufactured electrodes. The tortuosity, which strongly influences the ionic conductivity, is also presented for the analyzed electrodes, taking their microstructure into account.     

中间相炭微球在锂离子电池负极材料的应用进展

中间相炭微球(MCMB)具有良好锂离子扩散性、导电性和机械稳定性等优势,是目前应用广泛、综合性能优异的锂离子电池负极材料,但较低理论比容量是制约其发展的关键因素。为了获得性能优良的MCMB基锂离子电池负极材料,改性修饰和复合材料已然成为目前研发重点。笔者论述了碳结构、表界面和复合材料等微观结构设计对MCMB负极材料电化学性能的影响。从碳堆积结构类型、有序性、层间距以及球体粒径大小等方面,论述了碳结构微观设计对MCMB电化学性能的影响。发现具有乱层结构的MCMB在充放电过程中内部产生应力较小,且碳结构较稳定,具有优异循环稳定性;内部具有大量微孔或碳层间距较大的MCMB,在充放电过程中可提高锂离子在电极中的迁移速率,并提供更多的储锂空间,一般具有优良的充放电比容量和倍率性能;小粒径MCMB具有较短的锂离子迁移路径和随之增加的比表面积,通常具有较好倍率性能,伴随着可逆比容量和充放电效率的衰减。从表界面碳层改性、包覆和掺杂改性等方面,论述了表界面改性对MCMB电化学性能的影响。表面碳层修饰可增加MCMB与电解液的相容性及其比表面积,提高了与电解液的接触面积及贮锂容量,改善了锂离子电池负极材料的电化学性能;另外,MCMB表面包覆一层无定型碳,可避免其表面与电解液直接接触,减少电化学副反应的产生,提升其可逆比容量。从碳活性物质复合材料、非碳活性物质复合材料等方面,论述了复合材料微观结构设计对MCMB电化学性能的影响。碳活性物质可降低MCMB内部碳层结构的有序性,减少锂离子嵌入过程中的内部应力,提升MCMB循环稳定性。非碳活性物质诱导MCMB生成更加有序的碳层结构,提高MCMB的比表面积,从而改善MCMB表面与电解液分子的接触能力及其嵌锂性能,有利于提升MCMB负极材料可逆比容量、循环性能和倍率性能。MCMB具有高碳层间距和多缺陷位点等结构特征,有利于钠离子自由脱嵌,应用于钠离子电池时具有良好的可逆比容量、循环稳定性和倍率性能。MCMB的不规则定向层状结构经活化等处理具有较高比表面积,可应用于超级电容器电极材料。最后提出在高性能锂离子电池电极材料快速发展的需求下,从微观结构角度设计MCMB纳米复合材料将是MCMB负极材料的研究重点。     

Balancing the specific surface area and mass diffusion property of electrospun carbon fibers to enhance the cell performance of vanadium redox flow battery

Electrospun carbon fibers are featured with abundant electroactive sites but large mass transport resistances as the electrodes for vanadium redox flow battery. To lower mass transport resistances while maintaining large specific areas, electrospun carbon fibers with different structural properties, including pore size and pore distribution, are prepared by varying precursor concentrations. Increasing the polyacrylonitrile concentration from 9 wt% to 18 wt% results in carbonized fibers with an average fiber diameter ranging from 0.28 μm to 1.82 μm. The median pore diameter, in the meantime, almost linearly increases from 1.32 μm to 9.05 μm while maintaining the porosity of higher than 82%. The subsequent electroactivity evaluation and full battery testing demonstrate that the mass transport of vanadium ions through the electrode with larger fiber diameters are significantly improved but not scarifying the electrochemical activity. It is shown that the flow battery with these electrodes obtains an energy efficiency of 79% and electrolyte utilization of 74% at 300 mA cm⁻². Hence, all these results eliminate the concern of mass transport when applying electrospun carbon fibers as the electrodes for redox flow batteries and guide the future development of electrospun carbon fibers.     

Simple synthesis of graphitic nanotube incorporated cobalt nanoparticles for potassium ion batteries

Synthesis of novel electrodes is a critical step toward realizing rechargeable potassium-ion batteries (PIBs). In present study, the graphitic nanotubes (Co@GTs) implanted with cobalt nanoparticles were firstly fabricated by solid-state reaction. The results showed that in-situ synthesized Co@GTs composite network offered many active sites and provided channels for fast potassium ions transportation. Practical feasibility of the synthesized material has been confirmed by employing it as a positive electrode in potassium-ion batteries (PIBs). The Co@GTs composite exhibited a reversible capacity of 200 mAhg⁻¹ at the current density of 50 mA g⁻¹. Furthermore, the Co@GTs composite showed excellent cycle life, which may be attributed to the mesoscopic carbon substrate implanted with highly crystalized cobalt nanoparticles. This work highlights the capability of catalytic materials and their possibility to be used as a new class of anode materials for rechargeable metal-ion batteries.     

Highly stable graphene oxide composite proton exchange membrane for electro-chemical energy application

Proton exchange membrane is a basic element for any redox flow battery. Nafion is the only commercial available proton exchange membrane used in different electro-chemical energy systems. High cost restrict it's used for energy generation devices. In present work, we synthesised styrene divinylbenzene based composite proton exchange membranes (PEMs) with varying sulfonated graphene oxide (sGO) content for redox flow battery (RFB). Synthesized copolymer PEMs were analyzed in terms of their chemical structure with the help of FT-IR spectroscopy to confirm desired functional groups at appropriate position. Electrochemical characterization was performed in terms proton-exchange capacity, protonic conductivity and water uptake. Membrane shows adequate proton exchange capacity with good proton conductivity. Vanadium ion permeability was also tested for the prepared membrane to assess capability for vanadium redox flow battery (VRFB) in contrast with commercially available Nafion 117 PEM. Higher VO⁺² ion cross-over resistance was found for CEM-4 with 7.17 × 10⁻⁷ cm² min⁻¹ permeability, which is about half of the CEM-1. Further CEM-4 was also evaluated for charging-discharging phenomenon for single cell VRFB. The values of columbic, voltage and energy efficiency for VRFB confirms prepared membrane as a good candidate for redox flow battery. Composite PEM also shows better mechanical and thermal stability. Results indicates that synthesized composite membrane can be used in vanadium redox flow battery.     

退役电池回收产业现状及经济性分析

新能源汽车的快速发展使动力电池回收利用成为研究热点，但关于退役电池回收产业和经济性分析问题研究较少。研究了现阶段国内废旧电池回收产业现状及存在问题，对电池回收利用的经济性及生产经营过程产生的敏感性因素进行分析。同时指出电池回收技术的发展应以“退役动力电池资源再生-高值化锂电原材料”为主线，电池回收企业应积极与新能源汽车行业统筹协调发展、构建区域化回收利用体系、提升产业整体经济性水平，对动力电池回收行业具有一定的指导意义。     

Superior lithium storage performance of hierarchical N-doped carbon encapsulated NaTi2(PO4)3 microflower

Na-superionic conductor (NASICON) structured NaTi₂(PO₄)₃ (NTP) as anode shows broad prospect in aqueous lithium ion battery. However, inherent low electrical conductivity of NaTi₂(PO₄)₃ remains a pivotal issue to be resolved. Herein, we report N-doped carbon encapsulated NaTi₂(PO₄)₃ microflower (NTP-CN) as anode for aqueous lithium ion battery, which is prepared via solvothermal way. NTP-CN with unique structural feature displays superb electrochemical performances. It delivers the discharge capacities of 131.2, 110.1, and 84.3 mAh g⁻¹ at 0.2, 3.0, and 15 C, respectively, 38.8, 33.8, and 51.1 mAh g⁻¹ higher than these of pristine NTP. NTP-CN also shows remarkable cycling stability at 6 C after 1000 cycles (capacity retention: 88.8%), superior to NTP (70.7%). The outstanding properties of NTP-CN may be due to that microflower structure can increase touching area between electrolyte and electrode, and carbon coating for electrode improves stability in aqueous electrolyte and ameliorates electrical conductivity. Moreover, nitrogen doping can further enhance hydrophilicity and conductivity of the sample, and also form lots of defects on electrode surface, which is beneficial for the intercalation/deintercalation of Li ions. This work reveals that the combination of microflower structure and N-doped carbon layer offers a promising method to improve electrochemical performances of NaTi₂(PO₄)₃.     

Power and energy management of grid/PEMFC/battery/supercapacitor hybrid power sources for UPS applications

This paper presents a hybrid power and energy source supplied by a proton exchange membrane fuel cell (PEMFC) as the main power source in an uninterruptible power supply (UPS) system. To prevent the PEMFC from fuel starvation and degradation and realize their seamless linking in the hybrid UPS system, the power and energy are balanced by the battery and/or supercapacitor (SC) as two alternative auxiliary power sources. Based on the modeling and sizing of hybrid power and energy components, the power and energy management strategies and efficiency measurements of four operating modes in UPS system are proposed. To evaluate the proposed strategies, an experimental setup is implemented by a data acquisition system, a PEMFC generating system, and a UPS system including AC/DC rectifier, DC/AC inverter, DC/DC converter, AC/DC recharger and its intelligent control unit. Experimental results with the characteristics of a 300 W self-humidified air-breathing of PEMFC, 3-cell 12 V/5 Ah of batteries, and two 16-cell 120 F/2.7 V of SCs in parallel corroborate the excellent management strategies in the four operating modes of UPS system, which provides the basis for the optimal design of the UPS system with hybrid PEMFC/battery/SC power sources.     

Assessing Cloud Transient Impacts of Solar and Battery Energy Systems on Grid Inertial Responses

To assess the dynamic impact of intermittency of rapidly increasing solar photovoltaic generation on the grid, this article presents the modeling and integration of the components that need to be considered, including the solar photovoltaic plant, battery energy storage system, grid-tied interface, and associated control systems. The complexity and accuracy of these models are suitable for evaluating the transient impact on bulk power systems. Of particular interest is the grid inertial response in such situations as different penetration levels of solar generation and fast cloud transient induced solar generation decrease coupled with outages that recurrently occur in the grid, e.g., a generator trip. The impact of such events on the grid frequency responses is investigated using a simplified simulation approach to account for the locational or spatial irradiance variation patterns and cloud movements. Responsive battery energy storage systems are recognized as an effective means to improve the inertial response.     

苏通GIL运输专用机具动力电池类型探讨

GIL运输专用机具是为安全、可靠、高效地完成苏通GIL综合管廊工程GIL单元的运输任务而研制的专用机具,其中动力电池系统设计是整机设计的重点之一。通过对各种常见动力电池优缺点的分析,并结合苏通GIL运输专用机具对动力电池的需求分析,确定了动力电池系统的技术路线,为苏通GIL运输专用机具的研制提供了坚实的基础。