全固态钠离子电池及界面改性

全固态钠离子电池具有原料成本低、安全性高以及能量密度高等特点,在移动电源、电动汽车和大规模储能系统领域表现出巨大的应用潜力。然而全固态钠离子电池的发展和规模化应用亟需解决固体电解质室温离子电导率低、界面电荷转移阻抗大、固体电解质与电极界面兼容性和接触差等问题。本文结合近年来全固态钠离子电池相关报道和本课题组研究成果,概述了β-Al₂O₃型固体电解质、NASICON型固体电解质、硫化物固体电解质、聚合物固体电解质、复合固体电解质的研究进展及发展趋势;综述了全固态钠离子电池界面特性、固体电解质表面修饰、电极/固体电解质界面改性最新研究成果;最后对全固态钠离子电池界面改性策略发展方向进行了展望。本综述有助于加深对全固态钠离子电池界面科学问题的认识,并对固态钠离子电池的发展应用形成理论指导。     

无机钠离子电池固体电解质研究进展

地球上钠资源储量丰富、成本低廉,使得钠电池吸引了越来越多研究者的关注。传统的基于有机溶剂电解液体系的钠电池在安全方面存在不足。固态钠离子电池能够有效解决安全的问题,增加电池的安全性能。固态钠离子电池是一种很有前景的储能方式。钠离子固体电解质主要有Na-β-Al_2O_3、钠超离子导体(NASICON)、硫化物、聚合物以及硼氢化物这几类。无机固体电解质相对于聚合物固体电解质,离子电导率有优势。本文总结了三种常见的无机钠离子固体电解质:Na-β-Al_2O_3、NASICON、硫化物的研究进展,从离子电导率和界面稳定性等方面阐述了近年来的发展。     

锂硫银锗矿固态电解质研究进展

全固态电池因其较高的安全性和能量密度而成为下一代电动汽车和智能电网用储能器件的重点研究方向之一。开发具有高室温锂离子电导率、化学/电化学稳定性优异、对电极材料兼容性优异等特点的固态电解质材料是推动全固态电池发展的重要研究课题之一。硫化物电解质因其相对较高的室温电导率(~10⁻³ S∙cm⁻¹)、较低的电解质/电极固-固界面阻抗等优点而在众多无机固体电解质材料中成为研究热点。本文基于作者多年研究成果和当前国内外发表的相关工作,从电解质的结构、离子传导、合成、综合性能改善及在全固态电池中的应用等方面系统总结了锂硫银锗矿固态电解质材料研究,并分析了该类电解质面临的问题和挑战,最后探讨了其未来可能的研究方向和发展趋势。     

纳米石榴石固体电解质粉体在聚合物电解质中的均匀分散

固态锂电池(SSLBs)因采用金属锂负极和固体电解质,具有提高能量密度和安全性的潜质。固体电解质作为固态锂电池的关键材料,对电池性能有重要影响。其中,聚合物-石榴石型复合固态电解质因结合了聚合物电解质的易加工性以及石榴石电解质的热稳定性和高离子电导率的优点,在固态电池规模化制造中具有良好的应用前景。然而,由于纳米固体电解质粉体的表面能高、与有机物的界面兼容性差,导致纳米锂镧锆氧颗粒在聚合物基体中容易发生团聚,进而导致复合电解质的离子电导率降低。本工作引入硅烷偶联剂3-缩水甘油氧基丙基三甲氧基硅烷(GPTMS)对Li_6.4La₃Zr_1.4Ta_0.6O₁₂(LLZTO)的表面进行改性,旨在改善LLZTO颗粒在溶剂和聚合物基体中的分散性。LLZTO纳米颗粒表面的羟基与GPTMS分子反应形成共价键,在颗粒表面形成一层厚度约5 nm的GPTMS修饰层。GPTMS中具有亲脂性的环氧基团,使改性后的LLZTO纳米颗粒(LLZTO@GPTMS)在有机溶剂中均匀分散。粒度分布实验表明,LLZTO...     

固态聚合物电解质研究进展

开发下一代高安全且高能量密度能源体系是新能源产业进一步蓬勃发展的关键。将易燃易爆的液态电池替换为固态电池是一项极具前景的工作。在固态电解质中,聚合物电解质由于其高安全性、粘弹性及其良好的界面相容性等成为广泛研究的对象。但是在室温下其离子电导率仍然偏低,需要在高温下才能达到一定的电池性能。因此,在提升聚合物电解质常温离子电导率的同时,还需要进一步研究和改善电解质/电极之间的界面问题,降低界面阻抗。本文从固态聚合物的优缺点出发,介绍了不同固态聚合物电解质的性能及其离子传输机理,展望了固态聚合物电解质的最新研究进展和发展方向。     

高锂离子电导的有机-无机复合电解质的渗流结构设计

固态聚合物电解质被认为是解决传统液态锂金属电池安全隐患和循环性能的关键材料,但仍然存在离子电导率低,界面兼容性差等问题。近年来,基于无机填料与聚合物电解质的高锂离子电导的有机-无机复合电解质备受关注。根据渗流理论,有机-无机界面被认为是复合电解质离子电导率改善的主要原因。因此,设计与优化有机-无机渗流界面对提高复合电解质离子电导率具有重要意义。本文从渗流结构的设计出发,综述了不同维度结构的无机填料用于高锂离子电导的有机-无机复合电解质的研究进展,并对比分析了不同渗流结构的优缺点。基于上述评述,展望了有机-无机复合电解质的未来发展趋势和方向。     

旋涂法制备PEO-PAN-PMMA三组分共混凝胶聚合物电解质

随着新能源产业和储能产业的快速发展,二次电池的安全性和能量密度要求越来越高.而传统的液态锂电池使用易燃的电解液,所以存在较大的安全隐患.因此固态锂电池由于其较高的安全性和能量密度受到越来越多人的关注.目前困扰固态电池应用的主要问题是其离子电导率和电极电解质界面问题.固态电解质是固态电池的关键材料.因此开发高离子电导率的固态电解质是开发固态电池的关键.在本工作中,作者成功通过旋涂法制备聚乙二醇-聚丙烯腈-聚甲基丙烯酸甲酯（PEO-PAN-PMMA）凝胶电解质.PEO-PAN-PMMA聚合物薄膜为均匀透明的,具有较高的吸附率,且热稳定性较好,在380℃下保持稳定.通过浸泡电解液可以得到性能优异的凝胶电解质.该凝胶电解质具有较高的离子电导率,室温离子电导率为0.4 mS/cm,而且电化学窗口较宽,在0～4.2 V之间化学性能较为稳定,界面稳定性较好.组装成Li//PEO-PAN-PMMA凝胶电解质//LiCoO₂电池之后,正极首圈放电容量为129.8 mAh/g,循环100周,正极放电容量剩余119.51 mAh/g,在0.1 C、0.2 C、0.5 C和1 C倍率下循环,正极放电容量分别为129.8 mAh/g,99.5 mAh/g,86.1 mAh/g和64 mAh/g.     

固态电池无机固态电解质/电极界面的研究进展

全固态锂电池有望较好地提高电池安全性并实现高的能量密度,因此已成为二次锂电池发展的一个重要方向.发展具有高锂离子电导率、低电解质/电极界面阻抗及有较好应变性的固态电解质材料是全固态电池研究的重要研究课题.如何有效构筑电解质/电极界面,提高界面稳定性并显著降低界面阻抗又是其中的难点之一.本文综述了近年来国际上比较关注的两种无机固体电解质——硫化物与石榴石(garnet)型氧化物的最新研究进展,重点对这两类固体电解质与正负极材料的界面特性进行总结与评述.     

基于局部高盐界面润湿策略构筑的固态金属锂软包电池

固态金属锂电池因其优异的安全性和高的理论能量密度被认为是最具前景的下一代储能电池体系之一。随着以硫化物为代表的高离子导率电解质被逐渐开发,金属锂与固态电解质界面成为限制固态电池应用的主要瓶颈。金属锂/电解质的固固界面存在着界面接触差、界面电荷传输阻力高等问题。本文以固态金属锂软包电池为研究对象,通过由1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚、乙二醇二甲醚与双三氟磺酰亚胺锂组成的局部高盐液态电解液(HFE-DME LiTFSI)对金属锂/固态电解质界面进行润湿,增加金属锂与固态电解质之间的离子接触,降低离子传输阻力,从而提高锂离子在界面的传输能力。在30 mm×30 mm Li|Li4Ti5O12(LTO)固态软包电池中,通过3.0μL·cm^?2 HFE-DME LiTFSI局部高盐液态电解液润湿金属锂与固态电解质界面,软包电池的界面电阻从4366Ω·cm^?2降低到了64Ω·cm^?2。在0.1C与0.5C倍率下,LTO的放电比容量分别达到107与96 mAh·g^?1。同时,Li-S固态软包电池在0.01C及0.02C下,比容量也达到了1100与932 mAh·g^?1。     

石榴石结构Li7La3Zr2O12固态电解质掺杂改性研究进展

锂离子电池是目前发展最快的化学储能电源,使用固态电解质的固态锂离子电池相比传统液态电解质锂离子电池能量密度更高,安全性更好,是下一代锂离子电池的发展方向。石榴石结构Li₇La₃Zr₂O₁₂(LLZO)固态电解质凭借较高的离子电导率、宽的电化学窗口及优异的稳定性,成为了最具商业前途的固态电解质之一。本文从石榴石结构LLZO电解质的发展脉络出发,剖析了石榴石结构LLZO电解质的结构特性、离子传导机制及其具有的高的结构稳定性和离子传导能力的本源,在此基础上综述了石榴石LLZO电解质的单元、双元、多元体相掺杂改性以提升电解质本征离子电导率,第二相掺杂改性以提升电解质的抗锂细丝生长能力、陶瓷致密度等性能,最后对石榴石结构LLZO电解质材料掺杂改性方向进行了分析和展望,为推动全固态锂离子电池电解质的发展提供参考。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.