锂离子蓄电池正极材料LiFePO4研究进展

锂离子电池正极材料正在向着高比能量、长寿命、低成本、环境友好的方向发展,而具有橄榄石结构的LiFePO_4正极材料以其结构稳定、成本低、无污染等优点成为21世纪最理想的绿色电源,但自身也存在缺点。综述了锂离子电池正极材料LiFePO_4的研究进展。系统地阐述了LiFePO_4的晶体结构特征及性能、多种合成方法以及掺杂多种导电材料和控制晶体生长制备纳米粉体对材料性能的影响。对该材料的应用前景进行了展望,并提出了下一步可能的研究趋势。     

Preparation of safe water–lipid mixed electrolytes for application in ion capacitor

Aqueous electrolytes are safe, economic, and environmentally friendly. However, they have a narrow potential window. On the other hand, organic electrolytes exhibit good thermodynamic stability but are inflammable and moisture sensitive. In this study, we prepared water–PEG–lipid ternary electrolytes(TEs). To combine the advantages of water, polyethylene glycol(PEG) and propylene carbonate(PC). The nonflammable mixed electrolytes exhibited a wide potential window of about 2.8 V due to the beneficial effects of PEG and PC. Using these TEs, a lithium manganate–active carbon ion capacitor could be operated at 2.4 V with an energy density of 32 Wh/kg, based on the total active electrode material(current density of 3.3 m A/cm~2). This value was significantly higher than that achieved using an aqueous electrolyte, thereby rationalizing the higher energy density.     

高比能高功率全石墨烯锂离子电容器

石墨烯由于拥有超高比表面积和超高电导率而被作为电化学电容器材料广泛研究.本文采用树脂为碳源，通过一种方便快捷的树脂交换法制备一种具有高比表面积的多级孔三维石墨烯（3DG）.经过此种方法的催化、造孔、热处理等主要工艺步骤后，可显著增加石墨烯材料的小、介孔数量，从而提高材料的电化学性能.通过BET测试表明，3DG的比表面积可达2400 m²/g，孔体积达到2.0 cm³/g.以3DG作为正负极材料制备高比能量高功率型锂离子电容器（3DG-LIC），可使3DG-LIC的工作电压从传统超级电容器的2.5 V扩展到4.0 V，能量密度也从20 Wh/kg提高到105 Wh/kg.另外，相同的化学和微观结构能很好地平衡正负极的容量及速率，使高比能量高功率的3DG-LIC具有更宽阔的应用领域.     

高容量超级电容器电极材料的设计与制备

超级电容器寿命长,安全性高,并可以实现快速充放电,是化学电源研究的热点之一。然而,超级电容器的能量密度较低限制了其更多的应用。因此,超级电容器领域的研究关注点在如何提高超级电容器的能量密度。其中,提高比容量是提高能量密度的一种有效途径。本文通过对电极材料和电解液的优化来研究制备得到高容量超级电容器的方法。电极材料的比表面积、孔道结构和导电性对其电化学性能有着直接的影响。一方面,通过优化电极材料的孔道结构和比表面积可以增加活性位点并提高电解液离子传导率,从而得到高比电容。另一方面,电极材料导电性的提高有利于提升其电子传导率从而得到较高的比容量。本文分别对碳材料和金属氧化物/氢氧化物的优化达到了增加双电层电容和赝电容的目的。不仅如此,还可以通过在电解液中增加氧化还原电对从而得到高比电容。这一方法为高容量超级电容器的制备提供了新的思路。     

Co1−xFe2+xO4 (x = 0.1, 0.2) anode materials for rechargeable lithium-ion batteries

A cobalt-poor or iron rich bicomponent mixture of Co_0.9Fe_2.1O₄/Fe₂O₃ and Co_0.8Fe_2.2O₄/Fe₂O₃ anode materials have been successfully prepared using simple, cost-effective, and scalable urea-assisted auto-combustion synthesis. The threshold limit of lower cobalt stoichiometry in CoFe₂O₄ that leads to impressive electrochemical performance was identified. The electrochemical performance shows that the Co_0.9Fe_2.1O₄/Fe₂O₃ electrode exhibits high capacity and rate capability in comparison to a Co_0.8Fe_2.2O₄/Fe₂O₃ electrode, and the obtained data is comparable with that reported for cobalt-rich CoFe₂O₄. The better rate performance of the Co_0.9Fe_2.1O₄/Fe₂O₃ electrode is ascribed to its unique stoichiometry, which intimately prefers the combination of Fe₂O₃ with Co_1−xFe_2+xO₄ and the high electrical conductivity. Further, the high reversible capacity in Co_0.9Fe_2.1O₄/Fe₂O₃ and Co_0.8Fe_2.2O₄/Fe₂O₃ electrodes is most likely attributed to the synergistic electrochemical activity of both the nanostructured materials (Co_1−xFe_2+xO₄ and Fe₂O₃), reaching beyond the well-established mechanisms of charge storage in these two phases.     

Nanoporous silicon flakes as anode active material for lithium-ion batteries

Nanoporous-silicon (np-Si) flakes were prepared using a combination of an electrochemical etching process and an ultra-sonication treatment and the electrochemical properties were studied as an anode active material for rechargeable lithium-ion batteries (LIBs). This fabrication method is a simple, reproducible, and cost effective way to make high-performance Si-based anode active materials in LIBs. The anode based on np-Si flakes exhibited a higher performances (lower capacity fade rate, stability and excellent rate capability at high C-rate) than the anode based on Si nanowires. The excellent performance of the np-Si flake anode was attributed to the hollowness (nanoporous structure) of the anode active material, which allowed it to accommodate a large volume change during cycling.     

电化学石英晶体微天平研究高氯酸钠水溶液中活性炭电极的离子存储行为

以电化学石英晶体微天平(EQCM)为主要测试手段,在不同浓度的高氯酸钠(NaClO4)水溶液中研究了水合离子吸附到活性炭电极孔隙过程中电极的质量变化.对于每种电解液,根据Raman光谱和EQCM数据分别计算了本体溶液中和电极/溶液界面上Na+的水合数.通过比对这两组Na+水合数,探讨了Na+存储到活性炭负极过程中的去溶剂化效应.     

石墨烯包覆天然球形石墨作为锂离子电池的负极材料，是否需要乙炔黑导电剂？

我们通过包覆炭化的方法制备得到了石墨烯包覆的天然球形石墨(G/SG)材料,并使用扫描电子显微镜、X射线衍射仪以及多种电化学测试手段考察了不同石墨烯含量的复合材料的形貌结构及电化学性能。我们发现,在不添加乙炔黑(AB)的情况下,G/SG复合材料表现出较高的首次库伦效率,很好的循环稳定性和高倍率性能。当石墨烯包覆量为1%时,材料50次循环后的可逆容量可与添加10%AB的天然石墨电极(SG)等同;当石墨烯包覆量为2.5%时,材料的比容量完全高于添加10%AB的石墨电极。材料电化学性能的改善归因于石墨烯的包覆。一方面,石墨烯的柔软可变性可以保证天然石墨颗粒在充放电过程中的结构完整性,从而有效改善材料的循环稳定性;另一方面,石墨烯的存在提高了电极的导电性,促进更好导电网络的形成。因此,石墨烯包覆天然球形石墨材料中,石墨烯不仅是活性物质,也发挥导电剂的作用。当添加5%的乙炔黑时,在50 mA·g^-1电流循环50次后,5%G/SG电极的可逆容量从381.1 mAh·g^-1提高到404.5 mAh·g^-1,在1 A·g^-1电流时可逆容量从82.5 mAh·g^-1提高到101.9 mAh·g^-1,这表明G/SG电极仍然需要乙炔黑导电剂。乙炔黑颗粒填充在复合材料的空隙中,通过点接触的形式连接到G/SG颗粒,与石墨烯协同作用形成了更加有效的导电网络。尽管石墨烯包覆和乙炔黑添加对天然石墨电极具有积极的影响,例如增加了天然石墨电极的导电性和储锂性能(包括可逆容量,倍率性能和循环性能),但随着石墨烯或乙炔黑的增加,电极密度通常会降低。因此,在实际应用中应考虑石墨负极材料的质量和体积容量的平衡。这些结果对天然石墨的进一步商业应用具有重要意义。我们的工作为天然石墨电极在锂电池中的电化学行为提供了一种新的认识,并且有助于制备更高性能的负极材料。     

Electronic structure theory investigation on the electrochemical properties of cyclohexanone derivatives as organic carbonyl-based cathode material for lithium-ion batteries

Organic carbonyl-based compounds with redox-active site have recently gained full attention as organic cathode material in lithium-ion batteries (LIBs) owing to its high cyclability, low cost, high abundance, tunability of their chemical structure compared to traditionally used inorganic material. However, the utilization of organic carbonyl-based compounds in LIBs is limited to its poor charge capacity and dissolution of lower molecular weight species in electrolytes. In this study, we theoretically investigated five set of cyclohexanone derivatives (denoted as: H₁, H₂, H₃, H₄, and H₅) and influence of functional groups (-F and -NH₂) on their electrochemical properties using advanced level density functional theory (DFT) with the Perdew-Burke-Ernzenhof hybrid functional (PBE0) at 6-31+G(d,p) basis set. In line with the result gotten, the HOMO-LUMO results revealed that compound H₅ is the most reactive among the studied cyclohexanone derivatives exhibiting energy gap values of 0.552, 0.532, 0.772 eV for free optimized structures and structurally engineered structures with electron withdrawing group (EWG) and electron donating group (EDG) respectively. Also, results from electrochemical properties of the studied compounds lithiated with only one lithium atom displayed that compound H₂ exhibited interesting redox potential and energy density for all the studied structures in free optimized state (1108.28 W h kg^?1, 4.92 V vs Li/Li⁺), with EWG (648.22 W h kg^?1, 3.313 V Li/Li⁺), and with EDG (1002.4 W h kg^?1, 5.011 V vs Li/Li⁺). From our result, we can infer that compound H₂ and H₃ with corresponding redox potential, energy density and theoretical charge capacity value of 4.92 V vs Li/Li⁺, 1108.28 W h kg^?1, 225.26 mA h g^?1 and 5.168 V, 1041.61 W h kg^?1, 201.55 mA h g^?1 lithiated with only one lithium atom in free optimized state are the most suitable compounds to be employed as organic cathode material in lithium-ion batteries among all the investigated cyclohexanone derivatives.     

Nonflammable nonaqueous electrolytes for lithium batteries

As the energy density of state-of-the-art lithium (Li)-ion batteries (LIBs) increases, the safety concern of LIBs using liquid electrolytes is drawing increasing attention. Flammability of electrolytes is a critical link of the overall safety performance of LIBs and Li metal batteries. For this reason, intensive efforts have been devoted to suppressing the flammability of liquid electrolytes. In this short review, the common approaches to reduce the flammability of the nonaqueous liquid electrolytes will be summarized. The advantages and limitations of these approaches will also be discussed.