纳米颗粒的表面效应和电极颗粒间挤压作用对锂离子电池电压迟滞的影响

硅作为锂离子电池电极材料之一,其应力效应尤为突出,进而将影响电池性能.本文建立了电化学反应-扩散-应力全耦合模型,并研究了恒压充放电条件下扩散诱导应力、表面效应和颗粒间挤压作用对电压迟滞的影响.结果发现,应力及其导致的电压迟滞程度与颗粒尺寸相关.在大颗粒(颗粒半径r 100 nm)中,扩散诱导应力是导致电势迟滞效应的主要因素,这将导致电池能量耗散.对于纳米级小颗粒(r 100 nm)而言,表面效应占据主导,表面效应虽然能缓解电压迟滞,同时却会使驱动电化学反应部分的过电势回线下移,造成锂化容量衰减.本文综合考虑了扩散诱导应力和表面效应,得出:半径为10 nm的颗粒将会使电极具备较好的综合性能.此外,对于硅电极而言,颗粒间挤压作用会使应力回线向压应力状态演化,进而导致锂化容量的衰减.计算结果表明,在电极设计中,对孔隙率设定下限值有助于提升电极性能.     

Electrochemical performance of surfactant-processed LiFePO4 as a cathode material for lithium-ion rechargeable batteries

This study focuses on the effect of addition of surfactant as a dispersing agent during vibratory ball milling of LiFePO₄ (LFP) precursor materials on the electrochemical performance of solid-state reaction synthesized LFP for lithium-ion battery cathode material. LFP particles formed after calcinations of ball milled LFP precursors (Li₂CO₃, FeC₂O₄, and NH₄H₂PO₄) showed better size uniformity, morphology control, and reduced particle size when anionic surfactant (Avanel S-150) was used. The specific surface area of LFP particles increased by approximately twofold on addition of surfactant during milling. These particles showed significantly enhanced cyclic performance during charge/discharge due to a reduced polarization of electrode material. Electrodes fabricated from LFP particles by conventional milling process showed a 22 % decrease in capacity after 50 cycles, whereas the performance of electrode prepared by surfactant processed LFP showed only 3 % loss in capacity. The LFP particles were characterized using XRD, FE-SEM, particle size distribution, density measurement, and BET-specific surface area measurement. Electrochemical impedance spectra and galvanostatic charge/discharge test were performed for the electrochemical performance using coin-type cell.     

基于BC3NT的混合系锂空气电池正极第一性原理研究

文章采用第一性原理,利用掺杂硼的碳纳米管(BC₃NT)容易产生拓扑缺陷的特点,将其用作混合系锂空气电池正极材料,研究了BC₃NT拓扑缺陷电子性质及氧分子吸附.结果表明:BC₃NT产生的拓扑缺陷使得氧气在纳米管外表面吸附更加稳定,且缺陷环越大,吸附越稳定.七元环缺陷、八元环缺陷分别会使氧气在纳米管外表面发生半解离吸附和完全解离吸附,有利于氧还原反应的发生;通过布居分析电荷转移进一步验证了缺陷环越大,转移电荷越多,吸附越稳定. BC₃NT能增强对氧分子的解离吸附能力,有利于氧还原反应的进行.该材料适合用作混合系锂空气电池正极,有利于提高其性能.     

A dynamic capacity fading model with thermal evolution considering variable electrode thickness for lithium-ion batteries

Capacity is one of the key parameters to characterize the performances of lithium-ion batteries. Heat generation analysis is essential to evaluate the safety of batteries. To figure out the effects of electrode thickness on capacity fade and thermal behaviors, a capacity fading model is proposed considering reaction kinetics and mass transfer processes on solid electrolyte interface (SEI) layers coupled with thermal evolution. Simulations are conducted on seven LiFePO₄ batteries with variable electrode thicknesses. Results show that, with the increase of electrode thickness, the capacity losses of batteries deteriorate, and the total heat generation aggravates. For the battery with thick electrode, both the polarization overpotential and the gradient of lithium ion concentrations on particle surfaces of active materials increase on the edges, and then decrease perpendicularly to the cathodes. Under the adiabatic conditions, the temperature of battery (with anode 68 μm and cathode 140 μm) is increased to over 130 °C at the sixth cycle. The temperature of batteries declines when discharging in the beginning and then rises, which is noticeable for the batteries with thin electrodes. The proposed model and the simulation results would provide deep insights into both design and operation of batteries.     

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.     

集流体塑性变形对锂离子电池双层电极中锂扩散和应力的影响

针对锂离子电池双层电极结构,建立了综合考虑锂扩散、应力、浓度影响的材料属性及集流体弹塑性变形的理论模型.基于所建立的模型,主要研究了在充电过程中集流体可能发生的塑性变形对电极中锂扩散及应力的影响.数值结果表明集流体的塑性变形会减弱其对活性层的约束,这不仅使得集流体和活性层中的应力得到明显缓解,而且还促进了锂在活性层中的扩散,提高了活性层的有效容量.与此同时,研究了集流体的屈服强度和塑性模量这两个参数的影响,结果表明,较小的屈服强度和较小的塑性模量能进一步弱化约束,松弛电极活性层中的应力,并增加其有效充电容量.研究结果为分层电极的结构设计和性能优化提供了一定的参考.     

Comparison of electrochemical performance for zinc anode via various electrolytes and conducting agents in Zn-air secondary batteries

Zn-air batteries have many advantages as energy devices but they show a poor charge-discharge cycle performance. Therefore, this study examined the effects of various types of electrolytes and conducting agents and changed the additive contents to optimize the electrochemical performance of Zn-air secondary batteries. Electrolytes, such as sodium hydroxide (NaOH) and potassium hydroxide (KOH) solutions, and conducting agents, such as super-p, denka black, acetylene black, and ketjen black, were used to increase the electric conductivity. The electrochemical performance of the zinc anode was evaluated from charge-discharge capacities and cycle efficiency. When the capacity was compared according to each electrolyte from one to ten cycles, in contrast, the zinc anode in 6 M KOH showed a higher discharge capacity in the first cycle. Therefore, zinc anode was composed in the 6-M KOH electrolyte and conducting agents were added. The zinc anode included conducting agents with a higher cycle capacity than those without conducting agents, and super-p had a higher first discharge capacity than the others. Therefore, the zinc anode with super-p of 4% shows the highest performance using 6 M KOH in Zn-air secondary batteries.     

A facile pyrolysis method to prepare vanadium oxides for high performance aqueous Zn-ion battery

Vanadium oxides, as one of the most promising cathode materials for zinc ion batteries, have attracted extensive attention in recent years. Different from the generally used hydrothermal and solvothermal methods to adjust the composition, structure, morphology and electrical properties of vanadium oxides, we firstly adopt a simple pyrolysis method to synthesize a series of vanadium oxides and use them as cathode materials for aqueous Zn-ion battery, whose electrochemical performances is superior to most state-of-the-art vanadium oxides. The as-obtained V₄O₇ under the calcination temperature of 700 °C exhibits excellent zinc ion storage performance with maximum specific capacity of 367.2 mAh g⁻¹ at the current density of 1 A g⁻¹, about 84.9% capacity retention after 100 cycles, excellent rate performance, high capacity. In addition, a series of structural and electrochemical characterization are used to reveal the possible mechanism of charge and discharge.     

基于第一性原理的锂空气电池钌掺杂石墨烯正极 氧还原反应机理研究

双电解液锂空气电池因其高理论能量密度受到广泛研究,但电池正极侧氧还原反应(ORR)速率低,其反应速率是限制锂空气电池发展的主要因素之一.本文提出了以钌(Ru)掺杂单层石墨烯作为正极ORR催化剂,采用第一性原理计算nRu (n=1～3)掺杂石墨烯的电子结构和氧气在Ru掺杂石墨烯表面的吸附性能,并以过渡态搜索方法获得ORR反应路径,研究碱性溶液中Ru掺杂单层石墨烯作用下的ORR机理.研究结果表明,经Ru原子掺杂后,石墨烯能够获得稳定的掺杂结构,且电导率显著提升.同原始单层石墨烯相比,Ru掺杂石墨烯增强了对O₂的吸附能力.在三Ru(n=3)掺杂石墨烯表面进行的ORR无需克服任何能垒.此外,三Ru掺杂石墨烯表面对OH基团的吸附能最低,有利于ORR的连续进行.研究表明三Ru掺杂石墨烯有望成为一种新型的ORR催化剂以提高双电解液锂空气电池的性能.     

Electrochemical properties of modified acetylene black/sulfur composite cathode material for lithium/sulfur batteries

Lithium/sulfur (Li/S) batteries have a high theoretical specific capacity of 1672 mAh g^?1. However, the insulation of the elemental sulfur and polysulfides dissolution could result in poor cycling performance of Li/S batteries, thus restricting the industrialization process. Here, we prepared sulfur-based composite by thermal treatment. The modified acetylene black (H-AB) was used as a carrier to fix sulfur. The H-AB could interact with polysulfides and reduce the dissolution of polysulfides in the electrolyte. Nonetheless, the conductivity of H-AB relatively reduced. So the conductivity of the sulfur electrode would be improved by the addition of the conductive agent (AB). In this paper, the different content of conductive agent (AB) in the sulfur electrode was studied. The electrochemical tests indicate that the discharge capacity of the sulfur electrode can be increased by increasing the conductive agent (AB) content. The H-AB@S composite electrode with 30 wt.% conductive agent has the best cycle property. The discharge capacity still remains at 563 mAh g^?1 after 100 cycles at 0.1 C, which is 71% retention of the highest discharge capacity.     

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.     

S as additive in Mg–Cu<Subscript>2</Subscript>O seawater batteries using Ni foam-supported electrode

Cu₂O with S as additive electrode using Ni foam as the substrate is prepared in Mg–Cu₂O seawater battery. The morphology and electrochemistry performance of electrode are investigated. The excellent electrochemical properties of Ni foam-supported electrode indicate that it is suitable for seawater devices. The cell voltage of Mg–Cu₂O seawater batteries is elevated by sulphur addition. Sulphur participates in the electrochemical reactions; the elevation in cell voltage is 200–350 mV according to the ratio of Cu₂O to S.     

New layered metal oxides as positive electrode materials for room-temperature sodium-ion batteries

In order to achieve better Na storage performance, most layered oxide positive electrode materials contain toxic and expensive transition metals Ni and/or Co, which are also widely used for lithium-ion batteries. Here we report a new quaternary layered oxide consisting of Cu, Fe, Mn, and Ti transition metals with O3-type oxygen stacking as a positive electrode for room-temperature sodium-ion batteries. The material can be simply prepared by a high-temperature solidstate reaction route and delivers a reversible capacity of 94 m Ah/g with an average storage voltage of 3.2 V. This paves the way for cheaper and non-toxic batteries with high Na storage performance.     

Carbon-coated hollow CoO microporous nanospheres synthesized by CoF<Subscript>2</Subscript> as the intermediates as anode materials for lithium-ion batteries

Uniformly carbon-coated hollow CoO microporous nanospheres have been successfully synthesized by the facile hydrothermal method using CoF₂ as the intermediates and glucose as the carbon source. The whole synthesis process can avoid using the toxic surfactant additives and tedious post-processing. The glucose-derived carbon not only suppresses the aggregation of CoO nanoparticles, but also plays an important role on the stabilization of hollow CoO microporous nanosphere structure. The specific structure can largely improve the electronic conductivity and accommodate the volume change of CoO electrode in the electrochemical processes. When used as anode materials of lithium ion batteries, the hollow CoO/C microporous composites exhibit exceptionally high-rate performances, high-specific capacity, and improved cycle performances. This study may provide a new approach for the synthesis of carbon-coated hollow microporous architecture electrode for high-performance batteries.     

Cycle-life and degradation mechanism of LiFePO<Subscript>4</Subscript>-based lithium-ion batteries at room and elevated temperatures

Cycle-life tests of commercial 22650-type olivine-type lithium iron phosphate (LiFePO₄)/graphite lithium-ion batteries were performed at room and elevated temperatures. A number of non-destructive electrochemical techniques, i.e., capacity recovery using a small current density, electrochemical impedance spectroscopy, and differential voltage and differential capacity analyses, were performed to deduce the degradation mechanism of these batteries. To further characterize their internal materials, we disassembled the batteries, and material analyses were performed. All results indicated that loss in active lithium was the main reason for battery aging, and the cells showed diverse recession of active materials at different temperatures. In addition, high discharge rate and growing impedance lead to a capacity fall down at 25 °C at approximately 300–500 cycles.     

Reduced Graphene Oxide decorated with Manganese Cobalt Oxide as Multifunctional Material for Mechanically Rechargeable and Hybrid Zinc–Air Batteries

Spinel MnCo₂O₄ nanoparticles on nitrogen‐doped reduced graphene oxide (MnCo₂O₄/NGr) are synthesized for advanced zinc–air batteries with remarkable cyclic efficiency and stability. The synthesized MnCo₂O₄/NGr exhibits good oxygen‐reduction reaction (ORR) activity with half‐wave potential E _1/2 of 0.85 V (vs reversible hydrogen electrode (RHE)), comparable to commercial Pt/C with E _1/2 of 0.88 V (vs RHE) along with superior oxygen electrode activity ΔE = 0.91 V for the ORR/OER (oxygen‐evolution reaction) in alkaline media. Durability tests confirm that MnCo₂O₄/NGr is more stable than Pt/C in alkaline environment. MnCo₂O₄/NGr functions with stable discharge profile of 1.2 V at 20 mA cm^?2, large discharge capacity of 707 mAh g^?1_Zn at 40 mA cm^?2 and a high energy density of 813 Wh kg^?1_Zn in a mechanically rechargeable zinc–air battery. The electrically rechargeable MnCo₂O₄/NGr zinc–air battery displays hybrid behavior with both Faradaic and oxygen redox charge–discharge characteristics, operating at higher voltage and providing higher power density and excellent cyclic efficiency of 86% for over 100 cycles compared to Pt/C with efficiency of around 60%. Moreover, hybrid zinc–air battery operates with a stable and energy efficient profile at different current densities.     

High‐Capacity Anode Materials for Lithium‐Ion Batteries: Choice of Elements and Structures for Active Particles

Growing market demand for portable energy storage has triggered significant research on high‐capacity lithium‐ion (Li‐ion) battery anodes. Various elements have been utilized in innovative structures to enable these anodes, which can potentially increase the energy density and decrease the cost of Li‐ion batteries. In this review, electrode and material parameters are considered in anode fabrication. The periodic table is then used to explore how the choice of anode material affects rate performance, cycle stability, Li‐ion insertion/extraction potentials, voltage hysteresis, volumetric and specific capacities, and other critical parameters. Silicon (Si), germanium (Ge), and tin (Sn) anodes receive more attention in literature and in this review, but other elements, such as antimony (Sb), lead (Pb), magnesium (Mg), aluminum (Al), gallium (Ga), phosphorus (P), arsenic (As), bismuth (Bi), and zinc (Zn) are also discussed. Among conversion anodes focus is placed on oxides, nitrides, phosphides, and hydrides. Nanostructured carbon (C) receives separate consideration. Issues in high‐ capacity research, such as volume change, insufficient coulombic efficiency, and solid electrolyte interphase (SEI) layer stability are elucidated. Finally, advanced carbon composites utilizing carbon nanotubes (CNT), graphene, and size preserving external shells are discussed, including high mass loading (thick) electrodes and electrodes capable of providing load‐bearing properties.     

A novel binder-sulfonated polystyrene for the sulfur cathode of Li-S batteries

In order to suppress the capacity fading of lithium-sulfur batteries, sulfonated polystyrene (SPS) which was prepared via homogeneous reaction has been applied as a functional binder for the sulfur cathode of lithium sulfur batteries in this study. The SPS and its application for lithium sulfur batteries were characterized by Fourier transformation infrared spectroscopy (FT-IR), thermogravimetry (TG), X-ray diffraction (XRD), scanning electron microscopy (SEM), and charge-discharge test. The traditional binder poly vinylidene fluoride (PVDF) was used for comparison. Results show that for the sulfur cathode with PVDF as binder, the capacity retention after 100 cycles at 200 mA g^?1 is 46.9% and sever voltage fading performance from 10th to 100th cycle can be observed. While for SPS binder, the capacity retention after 100 cycles is 74.4% and there is almost no change of the first plateau at around 2.3 V in the discharge curve from 10th to 100th cycle, indicating obvious electrochemical performance improvement of lithium sulfur battery.     

电动汽车锂离子电池热管理系统研究进展

锂离子电池作为电动汽车最广泛使用的动力源,对工作温度高度敏感,为保证其高性能和安全运行,电池热管理系统必不可少.本文综述了近年来锂离子电池热管理系统的研究进展.首先讨论了由高低温环境和电池温度不均匀引起的临界热问题.在此基础上,对设计原则和现有的电池热管理系统进行了广泛的介绍和阐述.然后进一步分析了用于未来电池热管理系统的热电器件和内部加热方法等新兴技术.分析表明,被动和主动冷却/加热方法的组合有望满足苛刻的热要求,特别是在功率波动剧烈的动态条件下.此外,电池在变工况下所输出的电流、电压等均不相同,因此建议对电动汽车动力电池进行动态性能实时管理,从而延长电池使用寿命。     

Analysis of the Properties of Fractional Heat Conduction in Porous Electrodes of Lithium-Ion Batteries

Research on the heat transfer characteristics of lithium-ion batteries is of great significance to the thermal management system of electric vehicles. The electrodes of lithium-ion batteries are composed of porous materials, and thus the heat conduction of the battery is not a standard form of diffusion. The traditional heat conduction model is not suitable for lithium-ion batteries. In this paper, a fractional heat conduction model is used to study the heat transfer properties of lithium-ion batteries. Firstly, the heat conduction model of the battery is established based on the fractional calculus theory. Then, the temperature characteristic test was carried out to collect the temperature of the battery in various operating environments. Finally, the temperature calculated by the fractional heat conduction model was compared with the measured temperature. The results show that the accuracy of fractional heat conduction model is higher than that of traditional heat conduction model. The fractional heat conduction model can well simulate the transient temperature field of the battery. The fractional heat conduction model can be used to monitor the temperature of the battery, so as to ensure the safety and stability of the battery performance.