Effect of high adhesive polyvinyl alcohol binder on the anodes of lithium ion batteries

High molecular weight (MW) polyvinyl alcohol (PVA) was synthesized by two-step polymerizations and employed as an anodic binder of lithium ion batteries (LIBs). Numerous hydroxyl groups in PVA formed strong hydrogen bonds with both active materials and the current collector. These strong hydrogen bonds led to an increase in the amount of binder covering the surface of active materials and significantly enhanced the adhesion strength of electrodes. The high MW PVA binder showed much better cyclic performance for silicon/carbon anodes than polyvinylidene fluoride (PVDF) and polyacrylic acid (PAA) binders.     

New eco-friendly low-cost binders for Li-ion anodes

In the production of commercial Li-ion batteries, the active materials slurries are generally prepared using polyvinylidene fluoride (PVdF) as binder because of its good adhesion properties and electrochemical stability. Unfortunately, there are some disadvantages related to the use of PVdF: the most important is the use of toxic and environmentally unfriendly solvents, such as N-methyl-pyrrolidone (NMP), and the second is the high costs. In the light of these considerations, it seemed straightforward to investigate the suitability of some water-soluble, inexpensive, and eco-friendly materials to test as alternative binders (sodium alginate, chitosan tragacanth gum, gelatin). The rheological properties of these materials have been investigated in addition to the electrochemical characterization. Furthermore, graphite electrodes with PVdF, carboxymethyl cellulose (CMC), and styrene-butadiene rubber (SBR) binders have been considered for sake of comparison. We found that some of these water-soluble binders, besides good electrochemical performances, showed a high adhesion to the current collector and a good electrochemical stability under the experimental conditions employed, which makes them interesting for the next generation of Li-ion batteries.     

锂离子电池高电压正极粘结剂的研究进展

锂离子电池在高电压下会导致严重的电解液分解以及不稳定的正极与电解质界面问题,严重制约高电压正极材料的商业化.粘结剂不仅可以将正极活性材料和导电炭紧密粘结在集流体上,还对构建电解质与正极之间的多尺度相容性界面起积极作用,因此,粘结剂的优化可以有效解决上述难题.本文提出了高电压锂离子电池正极粘结剂需具备的必要条件,如:粘结...     

基于阵列电极的新型混合电容器

混合电容器由于兼具电池高能量密度和超级电容器高功率密度的优势,成为当前储能领域的研究热点。然而,电池电极和电容电极之间容量和功率的不平衡严重限制了混合电容器的实际性能。因此,如何实现二者的有效匹配,优化器件性能是混合电容器实用化的关键。阵列电极的使用打破传统粉末电极中不导电粘结剂对电化学动力学的限制,其独特的结构为正负极的匹配提供了新策略。此专论结合新型储能器件的研究现状以及本课题组在混合电容器方面的探索,简单探讨了混合电容器的储能机理和阵列结构作为电极材料的优势,着重介绍了本课题组近年来在混合电容器领域的研究工作,针对存在的科学问题提出了相应的解决方案,阐明了阵列电极混合电容器在柔性/可穿戴电子器件等领域的应用前景,并展望了混合电容器在未来的发展方向和挑战。     

有机磷酸酯阻燃电解液的研究进展

随着锂离子电池的市场拓展,安全性问题已成为电动汽车、大规模储能等应用领域关注的首要问题. 目前商品化的锂离子电池普遍采用低沸点碳酸酯类电解液,其易燃性成为电池不安全性的主要隐患. 为了提高锂离子电池的本征安全性,阻燃或不燃性电解液成为近年来研究的热点,其中以磷酸酯为溶剂的阻燃型或不燃型电解液受到广泛关注. 本文主要介绍磷酸酯阻燃和不燃电解液的研究状况,分析了这类电解液与锂离子电池正负极的兼容性问题,讨论了改善磷酸酯电解液电化学兼容性的途径,提出了发展高效、安全、稳定的不燃电解液的一些思路.     

Graphene and carbon nanotube composite electrodes for supercapacitors with ultra-high energy density

We describe a graphene and single-walled carbon nanotube (SWCNT) composite film prepared by a blending process for use as electrodes in high energy density supercapacitors. Specific capacitances of 290.6 F g(-1) and 201.0 F g(-1) have been obtained for a single electrode in aqueous and organic electrolytes, respectively, using a more practical two-electrode testing system. In the organic electrolyte the energy density reached 62.8 Wh kg(-1) and the power density reached 58.5 kW kg(-1). The addition of single-walled carbon nanotubes raised the energy density by 23% and power density by 31% more than the graphene electrodes. The graphene/CNT electrodes exhibited an ultra-high energy density of 155.6 Wh kg(-1) in ionic liquid at room temperature. In addition, the specific capacitance increased by 29% after 1000 cycles in ionic liquid, indicating their excellent cyclicity. The SWCNTs acted as a conductive additive, spacer, and binder in the graphene/CNT supercapacitors. This work suggests that our graphene/CNT supercapacitors can be comparable to NiMH batteries in performance and are promising for applications in hybrid vehicles and electric vehicles.     

粘结剂对形貌各异的石墨负极电化学性能的影响

As an important component in electrodes, the choice of an appropriate binder is significant when fabricating lithium-ion batteries (LIBs) with good cycle stability and rate capability, which are used in numerous applications, especially portable electronics and eco-friendly electric vehicles (EVs). Semi-crystalline poly(vinylidene fluoride) (PVDF), which is a traditional and widely used binder, cannot efficiently accommodate the volume changes observed in the anode during the charge-discharge process while binding all the components in the electrode together, which results in increased internal cell resistance, detachment of the electrode components, and capacity fading. Herein, we have investigated a highly polar and elastomeric polyacrylonitrile-butadiene (NBR) rubber for use as a binder in LIBs, which can accommodate graphite particles of different shapes compared to semi-crystalline PVDF. Prior to our electrochemical tests, NBR was analyzed using thermogravimetric analysis (TGA) and X-ray diffraction (XRD), showing good thermal stability and an amorphous morphology. NBR is more conformable to irregular surfaces, which results in the formation of a homogeneous passivation layer on both spherical and flaky graphite particles to effectively suppress any electrolyte side reactions, further allowing more uniform and fast Li ion diffusion at the electrolyte/electrolyte interface. As a result, the electrochemical performance of both spherical and flaky shape graphite electrodes was significantly improved in terms of their first cycle Coulombic efficiency (CE) and cycle stability. With comparative specific capacity, the first cycle CE of the NBR-based spherical and flaky graphite electrodes were 87.0% and 85.5%, compared to 85.3% and 82.6% observed for their corresponding PVDF-based electrodes, respectively. After 1000 discharge-charge cycles at 1C, the capacity retention of the NBR-based graphite electrodes was significantly higher than that of PVDF-based electrodes. This was attributed to the good stability of the solid electrolyte interphase (SEI) formed on the graphite electrodes and the high stretching ability of the elastomeric NBR binder, which help to accommodate the repeated volume fluctuation of graphite observed during long-term charge-discharge cycling. Electrochemical impedance spectroscopy (EIS) and microscopic analysis (SEM and TEM) were carried out to investigate the formation and evolution of the SEI layers formed on the spherical and flaky graphite electrodes. The results show that thin, homogeneous, and stable SEI layers are formed on the surface of both spherical and flaky graphite electrodes prepared using the NBR binder. When compared to the PVDF-based graphite electrodes, the graphite electrodes constructed using NBR showed decreased resistance in the SEI layer and faster charge transfer, thus enhancing the electrode kinetics for Li ion intercalation/deintercalation. Our study shows that the electrochemical performance of spherical and flaky graphite electrodes prepared using the NBR binder is significantly improved, demonstrating that NBR is a promising binder for these electrodes in LIBs.     

锂离子电池氧化亚硅负极结构优化和界面改性研究进展

氧化亚硅(SiO)作为锂离子电池负极材料,具有较高的理论比容量(~2043 mAh·g^-1)以及合适的脱锂电位(< 0.5 V),且原料储量丰富、制备成本较低、对环境友好,被认为是下一代高能量密度锂离子电池负极极具潜力的候选材料。然而,SiO在脱/嵌锂过程中存在着较严重的体积效应(~200%),易导致材料颗粒粉化、脱落,严重影响了SiO负极电极的界面稳定性和电化学性能。近年来,人们围绕SiO负极结构优化和界面改性开展了大量工作。本文先从SiO负极材料的结构特点出发,阐述了该材料面临的主要瓶颈问题;继而从SiO的结构优化、SiO/碳复合和SiO/金属复合等三方面,系统总结了迄今已有的SiO负极结构设计和界面调控策略,并分别对其方法特点、电化学性能以及二者间关联规律进行了比较和归纳,最后对SiO负极材料结构和界面改性的未来发展方向进行了展望。     

果胶粘结剂在锂硫电池中的应用研究

锂硫电池由于其超高理论能量密度(2567 Wh·kg^?1),较低的成本,以及环境友好性,被视为下一代储能设备的有力竞争者之一.鉴于粘结剂在稳定硫正极结构和抑制多硫化物穿梭方面可发挥重要作用,发展高性能硫正极粘结剂是改善锂硫电池性能的有效途径之一.本文研究了以果胶作为锂硫电池正极粘结剂的可行性.研究表明,采用果胶作为粘结剂的锂硫电池在电化学循环测试中首次放电比容量可达1210.6 mAh·g^?1,并且在200次循环后仍有837.4 mAh·g^?1的放电比容量,明显优于羧甲基纤维素钠-丁苯橡胶复合粘结剂的电池性能.经研究证实果胶粘结剂性能优良的原因在于其可以有效确保多壁碳纳米管/硫复合正极的结构稳定性并抑制多硫化物的穿梭.     

A High Performance Flocculating Agent and Viscosifiers Based On Cationic Guar Gum

The anionic, cationic and nonionic polymeric flocculants endowed with several distinguished characteristics are being increasingly applied for the treatment of industrial effluents, municipal and wastewater. For the treatment of highly negatively charged particle suspensions, cationic flocculants are more efficient. A new route to guar gum derivatives bearing cationic groups has been developed. A series of cationic guar gums (Cat GG) have been developed by incorporating a cationic moiety N- (3- Chloro-2- hydroxypropyl) trimethyl ammonium chloride (CHPTAC) onto the backbone of guar gum in presence of NaOH. The various grades of cationic guar gum have been characterized by elemental analysis, FTIR spectroscopy and intrinsic viscosity measurement. The flocculation characteristics of these cationic guar gums have been evaluated in silica suspension by jar test. It has been found that among the various grades of cationic guar gums, the one with longer CHPTAC chains shows better performance. The flocculation characteristics of this best performing cationic guar are compared with those of various commercially available flocculants in silica suspension. Their rheological investigations have also been undertaken.     

A Designed Durable Electrolyte for High-Voltage Lithium-Ion Batteries and Mechanism Analysis

Rechargeable lithium-ion batteries (LIBs) dominate the energy market, from electronic devices to electric vehicles, but pursuing greater energy density remains challenging owing to the limited electrode capacity. Although increasing the cut-off voltage of LIBs (>4.4 V vs. Li/Li⁺) can enhance the energy density, the aggravated electrolyte decomposition always leads to a severe capacity fading and/or expiry of the battery. Herein, a new durable electrolyte is reported for high-voltage LIBs. The designed electrolyte is composed of mixed linear alkyl carbonate solvent with certain cyclic carbonate additives, in which use of the ethylene carbonate (EC) co-solvent was successfully avoided to suppress the electrolyte decomposition. As a result, an extremely high cycling stability, rate capability, and high-temperature storage performance were demonstrated in the case of a graphite|LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) battery at 4.45 V when this electrolyte was used. The good compatibility of the electrolyte with the graphite anode and the mitigated structural degradation of the NCM622 cathode are responsible for the high performance at high potentials above 4.4 V. This work presents a promising application of high-voltage electrolytes for pursuing high energy LIBs and provides a straightforward guide to study the electrodes/electrolyte interface for higher stability.     

锂离子电池低温性能改善研究进展

锂离子电池因其能量密度高,循环寿命长等优点已成为新型动力电池领域的研究热点,但其温度特性尤其是低温性能较差制约着锂离子电池的进一步使用. 本文综述了锂离子电池低温性能的研究进展,系统地分析了锂离子电池低温性能的主要限制因素. 从正极、电解液、负极三个方面讨论了近年来研究者们提高电池低温性能的改性方法. 并对提高锂离子电池低温性能的发展方向进行了展望.     

Nicotinamide Adenine Dinucleotide Oxidation Studies at Multiwalled Carbon Nanotube/Polymer Composite Modified Glassy Carbon Electrodes

NADH oxidation has previously been investigated at carbon nanotube surfaces, although studies into the effect of the polymer binders are needed to fully understand whether the polymer binder affects the electrochemistry. This work details NADH oxidation at glassy carbon electrodes modified with composites containing multiwalled carbon nanotubes and selected polymer binders. NADH is shown to be oxidized at a lower potential than at glassy carbon electrodes and the oxidation potential is a function of the polymer binder. Hydrophobically modified Nafion, Nafion, linear poly(ethylenimine) (LPEI), octyl‐modified LPEI, and poly(vinylpyridine) binders were studied. Experiments showed the peak current and electrochemically assessible electrode area are dependent on the polymer binder. Overall, this paper shows that polymer binders affect NADH oxidation potential at carbon nanotube modified electrodes.     

Investigation of Water-Soluble Binders for LiNi0.5Mn1.5O4-Based Full Cells

Two water-soluble binders of carboxymethyl cellulose (CMC) and sodium alginate (SA) have been studied in comparison with N-methylpyrrolidone-soluble poly(vinylidene difluoride–co-hexafluoropropylene) (PVdF-HFP) to understand their effect on the electrochemical performance of a high-voltage lithium nickel manganese oxide (LNMO) cathode. The electrochemical performance has been investigated in full cells using a Li₄Ti₅O₁₂ (LTO) anode. At room temperature, LNMO cathodes prepared with aqueous binders provided a similar electrochemical performance as those prepared with PVdF-HFP. However, at 55 °C, the full cells containing LNMO with the aqueous binders showed higher cycling stability. The results are supported by intermittent current interruption resistance measurements, wherein the electrodes with SA showed lower resistance. The surface layer formed on the electrodes after cycling has been characterized by X-ray photoelectron spectroscopy. The amount of transition metal dissolutions was comparable for all three cells. However, the amount of hydrogen fluoride (HF) content in the electrolyte cycled at 55 °C is lower in the cell with the SA binder. These results suggest that use of water-soluble binders could provide a practical and more sustainable alternative to PVdF-based binders for the fabrication of LNMO electrodes.     

High safety separators for rechargeable lithium batteries

Lithium-ion batteries(LIBs) are presently dominant mobile power sources due to their high energy density, long lifespan, and low self-discharging rates. The safety of LIBs has been concerned all the time and become the main problem restricting the development of high energy density LIBs. As a significant part of LIBs, the properties of separators have a significant effect on the capacity and performances of batteries and play an important role in the safety of LIBs. In recent years, researchers devoted themselves to the development of various multi-functional safe separators from different views of methods, materials, and practical requirements. In this review, we mainly focus on the recent progress in the development of high-safety separators with high thermal stability, good lithium dendritic resistance, high mechanical strength and novel multifunction for high-safety LIBs and have in-depth discussions regarding the separator's significant contribution to enhance the safety and performances of the batteries. Furthermore, the future directions and challenges of separators for the next-generation high-safety and high energy density rechargeable lithium batteries are also provided.     

凝胶压井液用阴离子改性胍胶的制备及其流变性能

以环氧氯丙烷和NaHSO_3为原料,Na_2SO_3为引发剂,乙二胺四乙酸二钠(EDTA-2Na)为络合增效剂,经酸催化开环反应合成了磺酸型两性表面活性剂中间体3-氯-2-羟基丙磺酸钠,然后在弱酸性条件下与胍胶通过醚化反应制备了磺酸基羟丙基胍胶,其结构经IR表征。通过正交实验确定了合成配方和条件的最优结果,研究了反应温度、pH、改性胍胶浓度对成胶后凝胶的表观粘度影响,并测试了最佳条件下制备的凝胶和对应稀溶液的流变性能。结果表明:氧氯化锆可有效交联改性胍胶,在pH为6、温度为70℃、改性胍胶浓度为0.6%的条件下制备的凝胶具有剪切变稀性质以及较好的粘弹性。     

Strategies towards Low‐Cost Dual‐Ion Batteries with High Performance

Rocking‐chair based lithium‐ion batteries (LIBs) have extensively applied to consumer electronics and electric vehicles (EVs) for solving the present worldwide issues of fossil fuel exhaustion and environmental pollution. However, due to the growing unprecedented demand of LIBs for commercialization in EVs and grid‐scale energy storage stations, and a shortage of lithium and cobalt, the increasing cost gives impetus to exploit low‐cost rechargeable battery systems. Dual‐ion batteries (DIBs), in which both cations and anions are involved in the electrochemical redox reaction, are one of the most promising candidates to meet the low‐cost requirements of commercial applications, because of their high working voltage, excellent safety, and environmental friendliness compared to conventional rocking‐chair based LIBs. However, DIB technologies are only at the stage of fundamental research and considerable effort is required to improve the energy density and cycle life further. We review the development history and current situation, and discuss the reaction kinetics involved in DIBs, including various anionic intercalation mechanism of cathodes, and the reactions at the anodes including intercalation and alloying to explore promising strategies towards low‐cost DIBs with high performance.     

The effect of the binder morphology on the cycling stability of Li–alloy composite electrodes

It is demonstrated that the design of the composite electrode, or more precisely the morphology and distribution of the binder poly(vinylidine fluoride) (PVdF) within the composite electrode, has a significant impact on the cycling performance of Li storage alloy (Sn/SnSb) electrodes. Different binder morphologies and distributions have been obtained by using different solvents for the slurry preparation, such as 1-methyl-2-pyrrolidinone (NMP), in which PVdF is dissolved, yielding electrodes with a homogeneously and finely distributed binder, or decane, in which PVdF is only dispersed, yielding electrodes in which the original particle morphology of the binder powder is preserved. In constant current cycling tests carried out in an excess of electrolyte, the electrodes with the ‘dispersed’ binder show far better cycling capacities and stabilities than those with the ‘dissolved’ binder. This is explained by the different binding strengths, swelling behaviour in the electrolyte, electrode porosities, and possible ‘buffer’ effects of the compact and the finely distributed binders.     

锂离子电池硅基负极材料的最新研究进展

硅基材料因具有目前最高的理论比容量、合适的嵌锂平台、大储量等优点,引起了众多研究者的关注,成为最具潜力的下一代锂离子电池的负极材料. 但是硅在嵌锂过程中巨大的体积变化,容易破坏电极结构的稳定性,使电极循环性能迅速衰减,这对硅基材料的应用造成了很大的阻碍. 本文主要针对近年来在硅电极自身的结构（包括：多孔硅基复合材料的合成、硅粘结剂的选择,无粘结剂的纳米硅电极的制备）以及电解液添加剂的选择两大方面的最新研究进展进行总结与评述.     

Reducing the Charge Carrier Transport Barrier in Functionally Layer‐Graded Electrodes

Lithium‐ion batteries (LIBs) are primary energy storage devices to power consumer electronics and electric vehicles, but their capacity is dramatically decreased at ultrahigh charging/discharging rates. This mainly originates from a high Li‐ion/electron transport barrier within a traditional electrode, resulting in reaction polarization issues. To address this limitation, a functionally layer‐graded electrode was designed and fabricated to decrease the charge carrier transport barrier within the electrode. As a proof‐of‐concept, functionally layer‐graded electrodes composing of TiO₂(B) and reduced graphene oxide (RGO) exhibit a remarkable capacity of 128 mAh g⁻¹ at a high charging/discharging rate of 20 C (6.7 A g⁻¹), which is much higher than that of a traditionally homogeneous electrode (74 mAh g⁻¹) with the same composition. This is evidenced by the improvement of effective Li ion diffusivity as well as electronic conductivity in the functionally layer‐graded electrodes.