Functional copolymer binder for nickel-rich cathode with exceptional cycling stability at high temperature through coordination interaction

Nickel-rich layered oxide LiNi_(1-x-y)Co_(x)Al_yO_(2)(NCA) with high theoretical capacity is a promising cathode material for the next-generation high-energy batteries.However,it undergoes a rapid capacity fading when operating at high temperature due to the accelerated cathode/electrolyte interfacial reactions and adhesive efficacy loss of conventional polyvinylideneffuoride(PVdF) binder.Herein,poly(acrylonitrile-co-methyl acrylate) copolymer is designed with electron-rich-C≡N groups as a novel binder for LiNi_(0.8)Co_(0.1)Al_(0.1)O_(2) cathode at high temperature.The electron-rich-C≡N groups are able to coordinate with the active Ni^(3+) on the surface of NCA,alleviating electrolyte decomposition and cathode structure degradation.Moreover,the strong adhesive ability is conducive to maintain integrity of electrodes upon cycling at 55℃.In consequence,the NCA electrodes with this functional binder display improved cycling stability(81.5% capacity retention after 100 cycles) and rate performance at 55℃.

Revealing the working mechanism of a multi-functional block copolymer binder for lithium-sulfur batteries

The lithium-sulfur(Li-S)battery is one of the most promising substitutes for current energy storage systems because of its low cost,high theoretical capacity,and high energy density.However,the high solubility of intermediate products(i.e.,lithium polysulfides)and the resultant shuttle effect lead to rapidly fading capacity and a low coulombic efficiency,which hinder the practical application of Li-S batteries.In this study,block copolymers are constructed with both an ethylene oxide unit and a styrene unit and then used as binders for Li-S batteries.Electrochemical performance improvements are attributed to the synergistic effects contributed by the different units of the block copolymer.The ethylene oxide unit traps polysulfide,which bonds strongly with the intermediate lithium polysulfide,and enhances the transport of lithium ions to reach high capacity.Meanwhile,the styrene unit maintains cathode integrity by improving the mechanical properties and elasticity of the constructed block copolymer to accommodate the large volume changes.By enabling multiple functions via different units in the polymer chain,high sulfur utilization is achieved,polysulfide diffusion is confined,and the shuttle effect is suppressed during the cycle life of Li-S batteries,as revealed by operando ultraviolet-visible spectroscopy and S Kedge X-ray absorption spectroscopy.

Influence of Polymer Binder on the Physical Properties and Stability of Engineering Spoil on a Slope

An experiment was performed to study the influence of polymer binders on the physical properties,and stability against a simulated rainfall,of a slope consisting of engineering spoil.Results showed that low polymer binder concentrations(≤500g/m3) could enhance the air permeability and moisture-retaining capacity of the engineering spoil;however,adding more polymer binder made the hardness of the engineering spoil increase and then decline.With the increase of polymer binder concentrations,the surface(0-5cm) permeability of the engineering spoil decreased but the permeability of the lower layers(5-10cm) increased.Polymer binders might reduce runoff and sediment,but the effect becomes weaker with the increase of rainfall.The results of this study have significance for engineering practices.Further experiments are needed to study the effects of binders under other conditions,such as natural rainfall,different slopes,different rock types,different degrees and spoil weathering and different added material,and the chemical interaction between soil and polymer binders.

Design of multifunctional polymeric binders in silicon anodes for lithium‐ion batteries

Silicon(Si)is a promising anode material for lithium‐ion batteries(LIBs)owing to its tremendously high theoretical storage capacity(4200 mAh g−1),which has the potential to elevate the energy of LIBs.However,Si anodes exhibit severe volume change during lithiation/delithiation processes,resulting in anode pulverization and delamination with detrimental growth of solid electrolyte interface layers.As a result,the cycling stability of Si anodes is insufficient for commercialization in LIBs.Polymeric binders can play critical roles in Si anodes by affecting their cycling stability,although they occupy a small portion of the electrodes.This review introduces crucial factors influencing polymeric binders'properties and the electrochemical performance of Si anodes.In particular,we emphasize the structure–property relationships of binders in the context of molecular design strategy,functional groups,types of interactions,and functionalities of binders.Furthermore,binders with additional functionalities,such as electrical conductivity and self‐healability,are extensively discussed,with an emphasis on the binder design principle.

Alkali Metal Ion Substituted Carboxymethyl Cellulose as Anode Polymeric Binders for Rapidly Chargeable Lithium-Ion Batteries

The increasing demand for short charging time on electric vehicles has motivated realization of fast chargeable lithium-ion batteries(LIBs).However,shortening the charging time of LIBs is limited by Li^(+)intercalation process consisting of liquid-phase diffusion,de-solvation,SEI crossing,and solid-phase diffusion.Herein,we propose a new strategy to accelerate the de-solvation step through a control of interaction between polymeric binder and solvent-Li^(+)complexes.For this purpose,three alkali metal ions(Li^(+),Na^(+),and K^(+))substituted carboxymethyl cellulose(Li-,Na-,and K-CMC)are prepared to examine the effects of metal ions on their performances.The lowest activation energy of de-solvation and the highest chemical diffusion coefficient were observed for Li-CMC.Specifically,Li-CMC cell with a capacity of 3 mAh cm^(-2)could be charged to>95%in 10 min,while a value above>85%was observed after 150 cycles.Thus,the presented approach holds great promise for the realization of fast charging.

Advances of polymer binders for silicon-based anodes in high energy density lithium-ion batteries

Conventional lithium-ion batteries(LIBs)with graphite anodes are approaching their theoretical limitations in energy density.Replacing the conventional graphite anodes with high-capacity Si-based anodes represents one of the most promising strategies to greatly boost the energy density of LIBs.However,the inherent huge volume expansion of Si-based materials after lithiation and the resulting series of intractable problems,such as unstable solid electrolyte interphase layer,cracking of electrode,and especially the rapid capacity degradation of cells,severely restrict the practical application of Sibased anodes.Over the past decade,numerous reports have demonstrated that polymer binders play a critical role in alleviating the volume expansion and maintaining the integrity and stable cycling of Si-based anodes.In this review,the state-of-the-art designing of polymer binders for Si-based anodes have been systematically summarized based on their structures,including the linear,branched,crosslinked,and conjugated conductive polymer binders.Especially,the comprehensive designing of multifunctional polymer binders,by a combination of multiple structures,interactions,crosslinking chemistries,ionic or electronic conductivities,soft and hard segments,and so forth,would be promising to promote the practical application of Si-based anodes.Finally,a perspective on the rational design of practical polymer binders for the large-scale application of Si-based anodes is presented.

How Do Polymer Binders Assist Transition Metal Oxide Cathodes to Address the Challenge of High‑Voltage Lithium Battery Applications?

Research on the chemistry of high-energy-density transition metal oxide cathodes(TMOCs)is at the forefront in the pursuit of lithium-ion batteries with increased energy density.As a critical component of these cathodes,binders not only glue cathode active material particles and conducting carbons together and to current collectors but also play pivotal roles in building multiscale compatible interphases between electrolytes and cathodes.In this review,we outline several vital design considerations of high-voltage binders,several of which are already present in traditional binder design that need to be highlighted,and systematically reveal the chemistry and mechanisms underpinning such binders for in-depth understanding.Further optimization of the design of polymer binders to improve battery performance is also discussed.Finally,perspec-tives regarding the future rational design and promising research opportunities of state-of-the-art binders for high-voltage TMOCs are presented.

Compound Rejuvenation of Polymer Modified Asphalt Binder

The objective of this research was to show a way to conduct rejuvenation of aged polymer modified asphalt binder（PMB） successfully.To fully evaluate and understand the rejuvenation of aged PMB,the Penetration grade tests including penetration,soften point,ductility and elastic recovery and SuperpaveTM PG grade tests including DSR,BBR and DDT were conducted.The rejuvenation effect of aged PMB by utilizing a fluid recycling agent in common use for binder rejuvenation was evaluated.And then the compound rejuvenation effect of aged PMB by utilizing the recycling agent with a new modifying additive for binder modification was evaluated.The experimental results indicated that the recycling agent in common use currently does not apply to polymer modified asphalt binder rejuvenation.But the recycling agent together with the modifying additive can restore the characteristics of aged polymer modified binder very well.Therefore,compound rejuvenation of polymer modified asphalt binder is recommended.

Multifunctional binder designs for lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries are promising next-generation high energy density batteries but their practical application is hindered by several key problems,such as the intermediate polysulfide shuttling and the electrode degradation caused by the sulfur volume changes.Binder acts as one of the most essential components to build the electrodes of Li-S batteries,playing vital roles in improving the performance and maintaining the integrity of the cathode structure during cycling,especially those with high sulfur loadings.To date,tremendous efforts have been devoted to improving the properties of binders,in terms of the viscosity,elasticity,stability,toughness and conductivity,by optimizing the composition and structure of polymer binders.Moreover,the binder modification endows them strong polysulfide trapping ability to suppress the shuttling and decreases the swelling to maintain the porous structure of cathode.In this review,we summarize the recent progress on the binders for Li-S batteries and discuss the various routes,including the binder combination use,functionalization,in-situ polymerization and ion cross-linking,etc.,to enhance their performance in stabilizing the cathode,building the high sulfur loading electrode and improving the cyclic stability.At last,the design principles and the problems in further applications are also highlighted.

端羟基叠氮呋咱醚氧杂丁烷-HTPE嵌段共聚物合成及内增塑性能

针对增塑剂易迁移、渗出进而严重影响聚合物基复合材料物化性能和机械性能的问题,研究通过3-硝基-4-羟基呋咱与3,3-二溴甲基氧杂丁环(BBMO)偶联合成2种新单体3-(4-硝基呋咱-3-氧甲基)-3-溴甲基氧杂环丁烷(BrNFMO)、3,3-二(4-硝基呋咱-3-氧甲基)氧杂环丁烷(BNFMO),以端羟基聚醚(HTPE)为大分子引发剂,在三氟化硼乙醚催化下分别与BrNFMO、BNFMO以及对照组BBMO共聚后叠氮化,制备得到三种内增塑嵌段共聚物,对其进行结构、热分解行为、内增塑性能测试,并对所设计目标共聚单元进行量化计算以评估其爆轰性能。最后对共聚工艺进行了优化,通过“假活性”聚合策略对引入嵌段的程度进行控制。结果表明,该系列新型含能共聚单元具有优于现有叠氮基氧杂环丁烷单体的能量水平。与直接将叠氮基团引入聚合物相比,通过呋咱醚桥联结构将叠氮基团进行引入能够通过内增塑策略获得具有更低玻璃化转变温度T_(g)与黏度的含能共聚物(T_(g)可降低5.27℃,黏度可降低4.90 Pa·s),其热稳定性也得到了提高(T_(d)可提高7.3℃)。

Poly(thiourea triethylene glycol) as a multifunctional binder for enhanced performance in lithium-sulfur batteries

A mechanically strong binder with polar functional groups could overcome the dilemma of the large volume change during charge/discharge processes and poor cyclability of lithium-sulfur batteries(LSBs).In this work,for the first time,we report the use of poly(thiourea triethylene glycol)(PTTG)as a multifunctional binder for sulfur cathodes to enhance the performance of LSBs.As expected,the PTTG binder facilitates the high performance and stability delivered by the Sulfur-PTTG cathode,including a higher reversible capacity of 825 mAh g^(-1) at 0.2 C after 80 cycles,a lower capacity fading(0.123%per cycle)over 350 cycles at 0.5 C,a higher areal capacity of 2.5 mAh cm^(-2) at 0.25 mA cm^(-2),and better rate capability of 587 mAh g^(-1) at 2 C.Such superior electrochemical performances could be attributed to PTTG's strong chemical adsorption towards polysulfides which may avoid the lithium polysulfide shuttle effect and excellent mechanical characteristics which prevents electrode collapse during cycling and allows the Sulfur-PTTG electrode to maintain robust electron and ion migration pathways for accelerated redox reaction kinetics.

A flame-retardant binder with high polysulfide affinity for safe and stable lithium–sulfur batteries

Lithium-sulfur(Li-S) batteries have shown promises for the next-generation, high-energy electrochemical storage, yet are hindered by rapid performance decay due to the polysulfide shuttle in the cathode and safety concerns about potential thermal runaway. To address the above challenges, herein, we show a flame-retardant cathode binder that simultaneously improves the electrochemical stability and safety of batteries. The combination of soft and hard segments in the polymer framework of binders allows high flexibility and mechanical strength for adapting to the drastic volume change during the Li(de)intercalation of the S cathode. The binder contains a large number of polar groups, which show the high affinity to polysulfides so that they help to anchor active S species at the cathode. These polar groups also help to regulate and facilitate the Li-ion transport, promoting the kinetics of polysulfide conversion reaction. The binder contains abundant phosphine oxide groups, which, in the case of battery's thermal runaway, decompose and release PO· radicals to quench the combustion reactions and stop the fire. Consequently, Li-S batteries using the new cathode binder show the improved electrochemical performance, including a low-capacity decay of 0.046% per cycle for 800 cycles at 1 C and favorable rate capabilities of up to 3 C. This work offers new insights on the practical realization of high-energy rechargeable batteries with stable storage electrochemistry and high safety.

锂离子电池硅负极含氟粘结剂的制备与性能

合成了具有多重氢键网络结构的丙烯酸酯类粘结剂。结果表明,该含氟粘结剂装配的电池在4 A/g的电流密度下循环100圈后放电容量保持在1207 mAh/g,体积膨胀率为34.2%,具有较为优秀的电化学稳定性。其力学性能以及在循环过程中的自修复能力、SEI膜稳定性、容量保持率相较于常见商用粘结剂均有明显提升。

Design and Synthesis of Multi-Functional Polymeric Binders for High-Performance Lithium-Sulfur Batteries Based on Ring Opening Polymerization of Thiolactone

The application of high-performance lithium-sulfur(Li-S)batteries is severely influenced by the“shuttle effect”of polysulfides and the volume change of sulfur cathode.Herein,two different polymeric binders SOT-A and SOT-C with three-dimensional network structure containing polar groups(sulfhydryl groups,amide groups and amino groups)are synthesized by the nucleophilic ring-opening polymerization(ROP)of thiolactone with amino groups.The network structure formed by hydrogen bonds and functional groups can resist the volume change of the cathode.The sulfhydryl groups and the S-S bond formed by oxidative dehydrogenation of sulfhydryl group participate in the charge and discharge process of the battery as active materials,which improves the discharge specific capacity of the battery.Polar functional groups have strong chemisorption on polysulfides and effectively inhibit the“shuttle effect”.The electrochemical performances of Li-S batteries containing SOT-A and SOT-C binders are significantly enhanced.At 1 C rate,the batteries achieve initial discharge specific capacity of 871 and 837 mAh·g^(-1),respectively,and have 83.9%and 62.5%capacity retention after 500 cycles.

喷雾干燥法制备NTO/F2314微球及性能表征

为了调控3-硝基-1,2,4-三唑-5-酮(NTO)基高聚物黏结炸药的形貌和包覆效果,以细化NTO为主体炸药、偏氟乙烯和三氟氯乙烯共聚物(F2314)为包覆剂,采用喷雾干燥法制备了NTO/F2314复合微球,研究了喷雾干燥过程中进口温度、氮气流量、进料速率、料液固含量等工艺条件对NTO/F2314微球形貌的影响;利用场发射扫描电镜(SEM)、X射线光电能谱(XPS)、高分辨拉曼光谱(Raman)以及差式扫描量热(DSC)等测试方法,表征了微球形貌、结构及热分解特性。结果表明,制备NTO/F2314微球的优化工艺条件为:进口温度为80℃,氮气流量为414 L/h,进料速率为4.5 mL/min,料液固含量为2%;在此工艺下获得了形貌圆润、颗粒密实、包覆效果好的NTO/F2314复合微球,其热分解表观活化能为285.43 kJ/mol,相比细化NTO的表观活化能提升了16%,极大改善了NTO的热稳定性。

丙烯酸酯涂料印花粘合剂的合成及应用

采用无皂乳液聚合法合成了丙烯酸酯类涂料印花粘合剂NZ-071。讨论了各种因素对该涂料印花粘合剂性能及印花效果的影响,并得出了较佳合成工艺及织物整理工艺。结果表明,该涂料印花粘合剂稳定性良好,印花织物耐摩擦、皂洗等牢度好,手感柔软。

环保型印花粘合剂的辐射聚合及其性能研究

采用辐射聚合工艺制备出一种水性丙烯酸酯-聚氨酯涂料印花粘合剂。重点探讨了单体的影响,用红外光谱(IR)、透射电镜(TEM)对乳液进行了结构表征。并将其与常规乳液聚合法合成的产品进行了性能比较,结果表明:辐射聚合法合成的产品综合性能优于常规乳液产品。

Study on High Temperature Behaviour of Gussasphalt

Rutting is one of the most damages in the asphalt surfaces for the orthotropic steel bridge decks. With Hamburg wheel tracking device, the suitable test conditions for Gussasphalt in Germany are pointed out, the high temperature behaviour of Gussasphalt with different binders are tested and compared. The polymer modified binder has higher resistance stability to rutting. The retained time and mixed frequency have obvious effects on Gussasphalt behaviour during Gussasphalt retained period.

有机硅改性丙烯酸酯粘合剂的研制

以八甲基环四硅氧烷(D4)与含有乙烯基的有机硅烷偶联剂聚合,制得有机硅氧烷乳液,该乳液再与丙烯酸酯单体发生共聚反应,得到有机硅改性丙烯酸酯粘合剂.讨论了各种因素对乳液聚合的影响,应用结果表明:改性丙烯酸酯粘合剂稳定性能良好,处理后织物手感柔软、滑爽、无游离甲醛释放,是一种集柔软剂和粘合剂为一体的多功能印染助剂.

纺织品数码喷墨印花墨水的研究进展

介绍了纺织品数码喷墨印花技术的发展现状、原理和工艺,主要对喷墨印花墨水作了详细的分类介绍,并描述了国内外水性墨水和溶剂型墨水的研究现状,尤其对喷墨印花高分子染料墨水和油墨,以及喷墨印花颜料油墨用粘结剂作了详细的探讨。