A rechargeable battery based on hydrophilic radical polymer electrode and its green assessment

Abstract

A hydrophilic radical polymer electrode-based rechargeable battery was designed along the concept of green chemistry. A hydrophilic radical polymer, poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl vinylether), was synthesized as an electrode-active material; its battery demonstrated a high charging–discharging rate and long cycle life. The combination of the hydrophilic polymer electrode and an aqueous electrolyte for the battery fabrication was expected to provide safety improvements such as a low ignition risk besides the high battery performance. The green characteristics were studied using the “i-Messe,” an evaluation method proposed by the committee of the Green Sustainable Chemistry Network, Japan. The electrode-active polymer was evaluated for substantial improvements in disaster safety and health safety.     

All solid polymer electrolytes based on polar side group rotation for rechargeable lithium batteries

A novel polymer matrix with a polar carbonyl group was designed and used to prepare an all‐solid polymer electrolyte in lithium rechargeable batteries. The ionic conductivity of this type of polymer electrolyte was examined. The relationship between the lithium salt concentration and ionic conductivity was investigated by Fourier transform infrared (FTIR) spectroscopy. The carbonyl groups in the polymer matrix effectively interacted with the lithium salt, which improved the ionic conductivity at a large range of temperatures. The ionic conductivity of this type of polymer electrolyte was approximately 10^?4 S cm^?1 at room temperature. The stability of the interface between electrode and electrolyte was evaluated by measuring the alternating current (AC) impedance. Copyright © 2009 John Wiley & Sons, Ltd.     

锂及锂离子蓄电池有机溶剂研究进展

从有机溶剂对电池安全性的影响，氧化稳定性，与负极的相容性及对电解液电导率的影响四个方面，论述了锂及锂离子蓄电池有机溶剂的化学和电化学，介绍了碳酸酯类，醚类和羧酸酯类溶剂的性质与电极的相容性及在有机电解液中的应用，对含硫，硼基及胺类有机溶剂等也作了论述。     

A Redox-Active Microporous Organosiloxane Containing a Stable Neutral Radical,Trioxotriangulene

A new silyl-substituted trioxotriangulene ( TOT ) neutral radical and corresponding porous organosiloxanes (POSs) were synthesized. The neutral radical exhibited a peculiarly high stability and formed a diamagnetic π-dimer characteristic to TOT neutral radicals stabilized by the strong multiple SOMO-SOMO interaction in both solution and solid states. POSs including TOT units within the organosiloxane-wall were prepared by polycondensation of the silyl groups and formed microporous structures with ∼1 nm-size diameters. Redox ability of TOT units in the POS was demonstrated by the treatment of oxidant/reductant in heterogeneous suspension condition, where the TOT units were reversibly converted between reduced and neutral radical species. Furthermore, the solid-state electrochemical measurements of the POS revealed the reversible multi-stage redox ability of TOT units involving polyanionic species within the organosiloxane-wall.     

High capacity and cycling stability of poly(diaminoanthraquinone) as an organic cathode for rechargeable lithium batteries

Poly(1,5‐diaminoanthraquinone) is synthesized by oxidative polymerization of diaminoanthraquinone monomers and investigated as an organic host for Li‐storage reaction. Benefiting from its high density of redox‐active, Li⁺‐associable benzoquinone groups attached to conducting polyaniline backbones, this polymer undergoes its cathodic reaction predominately through Li⁺‐insertion/extraction processes, delivering a very high reversible capacity of 285 mAh g^?1. In addition, the PDAQ polymer cathode exhibits an excellent rate capability (125 mAh g^?1 at 800 mA g^?1) and a considerable cyclability with a capacity retention of ～160 mAh g^?1 over 200 cycles, possibly serving as a sustainable, high capacity Li⁺ host cathode for Li‐ion batteries. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 235–238     

Evaluation of Electrochemical Stability of Sulfonated Anthraquinone-Based Acidic Electrolyte for Redox Flow Battery Application

Despite intense research in the field of aqueous organic redox flow batteries, low molecular stability of electroactive compounds limits further commercialization. Additionally, currently used methods typically cannot differentiate between individual capacity fade mechanisms, such as degradation of electroactive compound and its cross-over through the membrane. We present a more complex method for in situ evaluation of (electro)chemical stability of electrolytes using a flow electrolyser and a double half-cell including permeation measurements of electrolyte cross-over through a membrane by a UV–VIS spectrometer. The method is employed to study (electro)chemical stability of acidic negolyte based on an anthraquinone sulfonation mixture containing mainly 2,6- and 2,7-anthraquinone disulfonic acid isomers, which can be directly used as an RFB negolyte. The effect of electrolyte state of charge (SoC), current load and operating temperature on electrolyte stability is tested. The results show enhanced capacity decay for fully charged electrolyte (0.9 and 2.45% per day at 20 °C and 40 °C, respectively) while very good stability is observed at 50% SoC and lower, even at 40 °C and under current load (0.02% per day). HPLC analysis conformed deep degradation of AQ derivatives connected with the loss of aromaticity. The developed method can be adopted for stability evaluation of electrolytes of various organic and inorganic RFB chemistries.     

A symmetric aqueous redox flow battery based on viologen derivative

Due to the diversity and feasibility of structural modification for organic molecules,organic-based redox flow batteries(ORFBs) have been widely investigated,especially in aqueous solution under neutral circumstance.In this work,a symmetric aqueous redox flow battery(SARFB) was rationally designed by employing a bipolar redox active molecule(N,N'-dimethyl-4,4-bipyridinium diiodide,MVI_2) as both cathode and anode materials and combining with an anion exchange membrane.For one MVI_2 flow battery,MV~(2+)/MV~(·+) and I~-/I_3~-serve as the redox couples of anode and cathode,respectively.The MVI_2 battery with a working voltage of 1.02 V exhibited a high voltage efficiency of 90.30% and energy efficiency of 89.44% after 450 cycles,and crossover problem was prohibited.The comparable conductivity of MVI_2 water solution enabled to construct a battery even without using supporting electrolyte.Besides,the bipolar character of MVI_2 battery with/without supporting electrolyte was investigated in the voltage range between-1.2 V and 1.2 V,showing excellent stable cycling stability during the polarity-reversal test.     

Fabrication of a Practical and Polymer‐Rich Organic Radical Polymer Electrode and its Rate Dependence

A practical and polymer‐rich organic radical cathode that contains 80 wt.‐% poly(4‐vinyloxy‐2,2,6,6‐tetramethylpiperidine‐N‐oxyl) (PTVE) and 15 wt.‐% vapor‐grown carbon fiber (VGCF) has been fabricated. The PTVE/VGCF composite electrode shows a reversible redox peak at 3.56 V (vs Li/Li⁺) in cyclic voltammetry. A coin‐type cell with the PTVE/VGCF composite electrode as the cathode and lithium metal as the anode has also been fabricated and used for charge/discharge measurements. When the cell was discharged at 0.3 mA · cm⁻² (1 C), a capacity of 104 mAh · g⁻¹, which is 77% of PTVE's theoretical capacity (135 mAh · g⁻¹), was obtained. When it was discharged at 9.0 mA · cm⁻² (30 C), its capacity was 52% of the capacity it had when it was discharged at 0.3 mA · cm⁻² (1 C). Even when discharged at 24 mA · cm⁻² (80 C), it surprisingly had 32% of the capacity it had when discharged at 0.3 mA · cm⁻². The observed rate dependence shows that the polymer‐rich electrode could discharge over 50% of the cell capacity in two minutes and over 30% within one minute.

     

Polymers Based on Stable Phenoxyl Radicals for the Use in Organic Radical Batteries

Polymers with pendant phenoxyl radicals are synthesized and the electrochemical properties are investigated in detail. The monomers are polymerized using ring‐opening metathesis polymerization (ROMP) or free‐radical polymerization methods. The monomers and polymers, respectively, are oxidized to the radical either before or after the polymerization. These phenoxyl radicals containing polymers reveal a reversible redox behavior at a potential of −0.6 V (vs Ag/AgCl). Such materials can be used as anode‐active material in organic radical batteries (ORBs).

     

Family Tree for Aqueous Organic Redox Couples for Redox Flow Battery Electrolytes: A Conceptual Review

Redox flow batteries (RFBs) are an increasingly attractive option for renewable energy storage, thus providing flexibility for the supply of electrical energy. In recent years, research in this type of battery storage has been shifted from metal-ion based electrolytes to soluble organic redox-active compounds. Aqueous-based organic electrolytes are considered as more promising electrolytes to achieve “green”, safe, and low-cost energy storage. Many organic compounds and their derivatives have recently been intensively examined for application to redox flow batteries. This work presents an up-to-date overview of the redox organic compound groups tested for application in aqueous RFB. In the initial part, the most relevant requirements for technical electrolytes are described and discussed. The importance of supporting electrolytes selection, the limits for the aqueous system, and potential synthetic strategies for redox molecules are highlighted. The different organic redox couples described in the literature are grouped in a “family tree” for organic redox couples. This article is designed to be an introduction to the field of organic redox flow batteries and aims to provide an overview of current achievements as well as helping synthetic chemists to understand the basic concepts of the technical requirements for next-generation energy storage materials.     

Organic Positive Materials for Magnesium Batteries: A Review

Magnesium batteries, like lithium-ion batteries, with higher abundance and similar efficiency, have drawn great interest for large-scale applications such as electric vehicles, grid energy storage and many more. On the other hand, the use of organic electrode materials allows high energy-performance, metal-free, environmentally friendly, versatile, lightweight, and economically efficient magnesium storage devices. In particular, the structural diversity and the simple activity of organic molecules make redox properties, and hence battery efficiency, easy to monitor. While organic magnesium batteries still in their infancy, this field becomes more and more promising because significant results were reported. To summarize the achievements in studies on organic cathodes for magnesium systems, their synthesis is discussed, combined with electrode design to provide the basis for controlling the electrochemical properties. Moreover, the techniques to synthesize organic materials with high-yield are mentioned. Finally, potential problems and prospects are explored to further improve organic cathodes.     

用于锂离子电池的聚合物电解质

本文主要依据最近5年来的相关文献，综述了锂离子电池用的聚合物电解质的研究进展。     

PVA碱性凝胶聚合物电解质薄膜电化学稳定性研究

应用溶解—铸膜法制备聚乙烯醇(polyvinylalcohol,PVA)碱性凝胶聚合物电解质(gelpolymerelectrolyte,GPE)薄膜.交流阻抗(EIS)测试表明,随着KOH含量的增加,该薄膜的离子电导率表现为先增大而后减小的变化趋势,当KOH含量为42%(bymass,下同)时,电导率达到最大值,为2.01×10-3S/cm.X射线衍射(XRD)结果表明,当膜中KOH含量大于20%时,晶态的PVA就逐渐转变为非晶态结构.又当KOH含量增加到一定值后,由于体系中未电离的非晶态KOH量的增多而导致离子电导率下降.循环伏安(CV)和拉曼光谱(Raman)结果表明,该薄膜具有很好的电化学稳定性,可应用于碱性二次电池.     

有机电极材料过渡态的研究进展

有机电极材料具有理论比容量大、结构可设计性强、加工使用过程环境友好等优点被广泛应用于二次电池的研究中.有机电极材料在氧化还原过程会产生具有不成对电子的自由基中间体,自由基中间体的稳定程度影响电极材料的电化学性能.通过改变材料的结构可以调控自由基中间体的稳定性,从而优化有机电极材料的电化学性能.本文对有机电极材料在电化学...     

The viscosity of aqueous electrolyte solutions and the TTG model

An equation covering the dynamic viscosity from zero to high concentrations has been derived on the basis of the TTG model. The equation is compatible with the Eyring andNMR theories and has a similar form to the Othmer-rule equation. A component of the limiting viscosity slope is shown to be proportional to the Falkenhagen slope. The TTG equation was tested for 20 electrolytes of diverse charge type and found to fit the data within the experimental errors. The equation is simply extended to cover pressure, temperature, and component changes. The viscosities of three multicomponent systems are predicted to within the experimental errors. The derived parameters of the equation were found to be simply related to the TTG volume of the solute.     

Grafting polyelectrolytes onto polyacrylamide for flocculation 1. Polymer synthesis and characterization

Low-molecular-weight high-charge-density cationic diallyldimethylammonium chloride homopolymer (polyDADMAC) was grafted onto high-molecular-weight nonionic polyacrylamide (PAM) via a free radical mechanism using a gamma radiation technique. The graft copolymer systems were characterized in terms of viscosity, composition, gel content, degree of grafting and grafting efficiency. Degree of grafting was a strong function of radiation dose, dose rate and polyelectrolyte concentration. Gels were formed at high radiation doses and high PAM levels. Crosslinking between the electrolyte polymers was limited due to electrostatic repulsion. Gelation was mainly caused by coupling of PAM chains. High grafting efficiency was achieved: the lower the poly(DADMAC) concentration, the higher the grafting efficiency observed. The grafting mechanism and the effect of ion interactions on copolymer structural properties are also elucidated and discussed. Received: 6 April 1998 Accepted in revised form: 28 August 1998     

LiMn2O4 nanorods as a super-fast cathode material for aqueous rechargeable lithium batteries

LiMn₂O₄ nanorods were prepared by a facile hydrothermal method in combination with traditional solid-state reactions and characterized by X-ray diffraction analysis. Their electrochemical behavior was tested by cyclic voltammetry and repeated charge/discharge cycling. Results show that the reversible intercalation/deintercalation of Li-ions into/from LiMn₂O₄ cathode can yield up to 110 mAh/g at 4.5 C, and still retains 88% at the very large charge rate of 90 C with well-defined charge and discharge plateaus. It presents very high power density, up to 14.5 kW/kg, and very excellent cycling behavior, 94% capacity retention after 1200 cycles. It is thus a competitor for LiFePO₄.     

固态聚合物电解质的锂离子传导机理与研究进展

锂离子电池(lithiumionbatteries,LIBs)在储能领域已取得了巨大的成功.然而,商用LIBs含有高挥发性易燃有机电解液,使其存在严重的安全隐患.固态聚合物电解质具有解决相应安全性问题的潜力,有望成为下一代高安全性全固态LIBs的电解质材料.然而,固态聚合物电解质存在离子电导率不高等问题,限制了其在固态LIBs中的实际应用.研究者们为了提高该类电解质的离子电导率、锂离子迁移数等综合电化学性能,已在寻找新锂盐、对聚合物进行改性以及向聚合物电解质中添加填料等方面进行了较多的研究.本文简要概述了固态聚合物电解质的锂离子传导机理以及在提高固态聚合物电解质综合电化学性能方面的研究进展.     

Synthesis of nitroxide‐containing block copolymers for the formation of organic cathodes

This contribution describes the polymerization of 2,2,6,6‐tetramethylpiperidin‐4‐yl methacrylate by atom transfer radical polymerization (ATRP). Different catalytic systems are compared. The CuCl/4,4′‐dinonyl‐2,2′‐dipyridyl catalytic system allows a good control over the polymerization and provides polymers with a polydispersity index below 1.2. The successful polymerization of styrene from PTMPM‐Cl macroinitiators by ATRP is then demonstrated. Successful quantitative oxidation of PTMPM‐b‐PS block copolymers leads to poly(2,2,6,6‐tetramethylpiperidinyloxy‐4‐yl‐methacrylate)‐b‐poly(styrene) (PTMA‐b‐PS). The cyclic voltammogram of PTMA‐b‐PS indicates a reversible redox reaction at 3.6 V (vs. Li⁺/Li). Such block copolymers open new opportunities for the formation of functional organic cathode materials. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013