An asymmetric bilayer polymer-ceramic solid electrolyte for highperformance sodium metal batteries

Manufacturing an excellent solid electrolyte compatible with a high-voltage cathode is viewed as a critical tactic for improving the energy density of solid-state sodium-ion batteries(SSIBs).A novel asymmetric bilayer solid electrolyte of the PEO-SN-NaClO_(4)|NZSP-NSO with an anti-reduction PEO-SN-NaClO_(4)layer close to the Na side is constructed by solution casting.The ionic conductivity is enhanced by using succinonitrile(SN)in polyethylene oxide(PEO)polymer electrolyte.The anti-oxidation layer of Na_(3)Zr_(2)Si_(2)PO_(12)with Na_(2)SiO_(3)(NZSP-NSO)is served as the support of the membrane on the cathode,which could improve the interface compatibility and electrochemical performance of SSIBs.The asymmetric bilayer solid electrolyte simultaneously features a wide electrochemical stability window(4.65 V vs.Na+/Na)and a high conductivity(2.68×10^(-4) S cm^(-1)).Furthermore,the solid electrolyte demonstrates stable Na plating/stripping over 700 h and remarkably improves cycling stability in Na/Na_(3) V_(2)(PO_(4))_(3) batteries with an ultra-high capacity retention of 99.6%after 100 cycles at 50℃and 0.5 C.This study provides an effective strategy for designing asymmetric high sodium ion conductivity solid-state electrolytes for high-performance SSIBs.

A novel surface molecularly imprinted polymer as the solid-phase extraction adsorbent for the selective determination of ampicillin sodium in milk and blood samples

Surface molecularly imprinted polymers （SMIPs） for selective adsorption of ampicillin sodium were synthesized using surface molecular imprinting technique with silica gel as a support. The physical and morphological characteristics of the polymers were investigated by scanning electron microscope （SEM）, Fourier transform infrared spectroscopy （FT-IR）, thermogravimetric analysis （TGA）, elemental analysis and nitrogen adsorption-desorption test. The obtained results showed that the SMIPs displayed great adsorption capacity （13.5 lag/mg）, high recognition ability （the imprinted factor is 3.2） and good binding kinetics for ampicillin sodium. Finally, as solid phase extraction adsorbents, the SMIPs coupled with HPLC method were validated and applied for the enrichment, purification and determination of anapicillin sodium in real milk and blood samples. The averages of spiked accuracy ranged from 92.1% to 107.6%. The relative standard deviations of intra- and inter-day precisions were less than 4.6%. This study provides a new and promising method for enriching, extracting and determining ampicillin sodium in complex biological samples.

Development of solid-state electrolytes for sodium-ion battery–A short review

All-solid-state sodium-ion battery is regarded as the next generation battery to replace the current commercial lithium-ion battery, with the advantages of abundant sodium resources, low price and high-level safety. As one critical component in sodium-ion battery, solid-state electrolyte should possess superior operational safety and design simplicity, yet reasonable high room-temperature ionic conductivity. This paper gives a comprehensive review on the recent progress in solid-state electrolyte materials for sodium-ion battery, including inorganic ceramic/glass-ceramic, organic polymer and ceramic-polymer composite electrolytes, and also provides a comparison of the ionic conductivity in various solid-state electrolyte materials. The development of solid-state electrolytes suggests a bright future direction: all solid-state sodium-ion battery could be fully used to power all electric road vehicles, portable electronic devices and large-scale grid support.

Solid State Characterization of Sodium Eritadenate

Knowledge of the solid state is of great importance in the development of a new active pharmaceutical ingredient, since the solid form often dictates the properties and performance of the drug. In the present study, solid state characteristics of the sodium salt of the candidate cholesterol reducing compound eritadenine, 2(R), 3(R))-dihydroxy-4-(9-adenyl)-butanoic acid, were investigated. The compound was crystallized by slow cooling from water and various aqueous ethanol solutions, at different temperatures. Further, the compound solution was subjected to lyophilization and to high vacuum drying. The resulting solids were screened for polymorphism by micro Raman spectroscopy (λex = 830 nm) and the crystallinity was investigated by X-ray powder diffraction. Further, thermal analysis was applied to study possible occurrence of solvates or hydrates. Solids obtained from slow cooling showed crystallinity, whereas rapid cooling gave rise to more amorphous solids. Analysis of difference spectra of the Raman data for solids obtained from slow cooling of solution revealed subtle differences in the structures between crystals derived from pure water and crystals derived from aqueous ethanol solutions. Finally, from the thermal analysis it was deduced that crystals obtained from pure water were stoichiometrically dihydrates whereas crystals obtained from aqueous ethanol solutions were 2.5 hydrates;this formation of different hydrates were supported by the Raman difference analysis.

Composite solid electrolyte of Na3PS4-PEO for all-solid-state SnS2/Na batteries with excellent interfacial compatibility between electrolyte and Na metal

High ionic conductivity and superior interfacial stability of solid electrolytes at the electrodes are crucial factors for high-performance all-solid-state sodium batteries. Herein, a composite solid electrolyte Na3PS4-polyethylene oxide is synthesized by the solution-phase reaction method with an improved ionic conductivity up to 9.4 × 10-5 S/cm at room temperature. Moreover, polyethylene oxide polymer layer is wrapped homogeneously on the surface of Na3PS4 particles, which could effectively avoid the direct contact between Na3PS4 electrolyte and sodium metal, thus alleviate their side reactions. We demonstrate that all-solid-state battery SnS2/Na with the composite solid electrolyte Na3PS4-polyethylene oxide delivers an enhanced electrochemical performance with 230 m Ah/g after 40 cycles.

Wet carbon-based solid acid/NaNO_3 as a mild and efficient reagent for nitration of aromatic compound under solvent free conditions

Nitro aromatic compound can be obtained in high yields via nitration of aromatic compound with wet carbon-based solid acid and NaNO_3 under solvent free oxidation at room temperature.

Determination of trace calcium by solid substrate-room temperature phosphorimetry

A new method for the determination of trace calcium by solid substrate-room temperature phosphorimetry is established. It is based on the fact that chromeazurols azurol S-phenanthroline-NaCMC (CAS-phen-NaCMC) system can emit strong and stable room temperature phosphorescence (RTP) on the solid substrate in the filter paper. Ca(2+) and phenanthroline can form complex ion Ca(phen)3(2+), which will form complex [Ca(phen)3(CAS)2] with CAS. In the result, the number of CAS molecules in each spot increased, causing sharp increase of the RTP signal of the CAS-phen-NaCMC system.

基于Na-BP-DME@C阳极的长寿命准固态钠-空气电池

钠-空气电池因其能量密度高、成本低而成为金属-空气电池领域的研究热点。然而,以金属钠为阳极的钠-空气电池存在钠枝晶生长、金属钠界面稳定性差以及金属钠的反应活性高等问题,限制了钠-空气电池的快速发展。为解决上述问题,将联苯钠与导电炭黑复合材料Na-BP-DME@C作为阳极,单壁碳纳米角(SWCHNs)作为催化剂,构建准固态钠-空气电池。基于Na-BP-DME@C阳极的准固态钠-空气电池表现出优异的电化学性能,其电压差为1.5 V,功率密度为3.32 mW/cm^(2),在0.1 mA/cm^(2)电流密度下可稳定循环459 h(约459次)。

Synthesis and Conductivity Characterization of Anti-Perovskite Na3OX Solid Electrolytes for All Solid Na-Ion Batteries

Solid electrolytes for all solid sodium-ion batteries have been attracting much attention as an alternative energy storage system, which have the advantage of being extremely safe because it can be charged quickly and is nonflammable. We have synthesized anti-perovskite type Na3OX (X = Br, and I) electrolytes with high purity, by reactions of halogen mixtures with sodium oxides. After mixing, it was filled in an alumina crucible and heated for 6 hours at 330°C. It was confirmed that a large crystal strain was introduced by eutectication, which might reduce the activation energy of Na ion conduction and lead to an improvement of the conductivity. A relatively higher ionic conductivity of σ = 1.55 × 10-7 S/cm at 60°C has been obtained for Na3OBr0.6I0.4, which is about three orders higher than that in literature. A different ratio of X (X = Br, I) ions was added into sodium oxide to make the Na3OX crystal. The influence of strain introduction on optimizing the bottleneck and improving the conductivity was discussed.

普鲁士蓝类钠电池正极生产废水预处理工艺研究

钠离子电池作为新兴产业,有关其生产工艺的研究较多,但是鲜少见到关于钠电池生产废水处理工艺的研究。因此,本文对普鲁士蓝类钠电池正极废水的预处理工艺进行实验研究,探究最佳处理工艺。最终确定了母液废水采用直接氧化法预处理工艺,即先加入H_(2)O_(2)(1.18倍理论投入量),然后用质量分数为30%的NaOH溶液调pH至9左右,静置30 min,再经过管式超滤膜过滤,母液中铁锰元素的去除率分别约为99.93%和99.99%。洗水废水采用两段式沉淀法预处理工艺,即第一阶段采用固氰除铁法,先用质量分数为30%的NaOH溶液调pH至7左右然后加入硫酸亚铁(硫酸亚铁投入量与废水中铁元素质量比为5.2),反应静置30 min。主要去除废水中绝大部分的铁元素和少部分锰元素。在一段处理的基础上再采用氧化沉淀法,先加入H_(2)O_(2)(0.83倍理论投入量),然后用质量分数为30%的NaOH溶液调pH至9,反应静置30 min,再经过管式超滤膜过滤,最终铁和锰元素的去除率分别约为99.87%和99.99%。为实际工程中钠电池废水预处理提供了重要技术参考。

MOFs基固体电解质在钠离子电池中的应用进展

传统钠离子电池常使用液体有机电解质,存在热失控等安全问题。而固态电解质具有高安全性和高能量密度,因而成为下一代储能设备材料最有潜力的候选者。金属有机骨架(MOFs)由金属节点和有机连接器构成,具有高孔隙率、高比表面积和有序孔道,是设计快速离子导电材料的一个很有前途的结构平台。基于MOFs结构的多样性和可修饰性,介绍几种导钠离子MOFs基固体电解质的研究设计,包括引入掺杂相应阴离子钠盐的离子液体或有机溶剂、钠化处理、枝接与电解质离子相互作用的官能团和与聚合物复合的杂化材料。

Development and Demonstration of Australian First Working Sodium Guide Star Laser

The Australian first working sodium guide star laser system has been designed and developed for various astronomical and space-related applications. A completely diode-pumped pulsed system was developed initially followed by a largely fiber-based continuous wave (CW) system operating at 589 nm achieved through a unique wavelength conversion scheme by combining 1342 and 1050 nm through a sum frequency generation process. For the CW system, single-mode laser beams at both 1342 and 1050 nm are achieved from fiber-based seed oscillators and fiber amplifiers. The output power of ~25 W at 1342 nm is achieved from a single frequency fiber Raman amplifier. Output power up to 70 W at 1050 nm is achieved from a Yb-doped fiber pre-amplifier followed by a Yb-doped fiber power amplifier. For the sum frequency generation process, optimum focusing parameters are evaluated and determined. The CW system has generated more than 20 W output power at 589 nm, a circularly polarised beam with a good beam quality, spectral linewidth ≤ 2 MHz, and the laser output locked on the sodium D2 line at 589.159 nm. The system has been successfully demonstrated at EOS Space Research Centre, Mt Stromlo, Canberra, and become the Australian first working sodium guide star laser system.

新型储能技术进展与挑战I:电化学储能技术

新型储能技术日益成为中国建设新型能源体系和新型电力系统的关键技术,已成为中国经济发展的新动能,将在促进可再生能源消纳、实现能源体系转型、提高能源利用效率、减少环境污染等方面发挥重要作用,相关技术研究也在快速发展。开展了该领域的系列评价性综述工作,分为电化学储能技术、物理储能与储热技术、储能集成与规划3个部分,对各类新型储能技术的应用领域、最新研究进展及局限性等问题进行了全面系统的对比分析,并进一步探讨了储能集成、安全、规划调度等储能系统相关领域面临的挑战及发展趋势。第1部分为电化学储能技术,重点对锂离子电池、钠离子电池、液流电池、固态电池和水系电池的技术与工程的相关成果进行了综合分析与讨论。电化学储能技术具有灵活配置的特点,可以满足不同功率和能量的应用需求,锂离子电池技术的成熟度最高,在储能市场占有主体地位,未来进一步发展集中于系统集成和安全技术方面,以推进更大规模的商业化应用。其他一些尚处于基础研究阶段的电池技术也展现出了巨大的发展潜力,比如:固态电池具有更高的安全性,钠离子电池具有优越的低温性能,液流电池具有较长的循环寿命等。

采用固体硅酸钠激发的一步法地质聚合物在软土固化中的适用性研究

为解决水泥固化软土早期强度不足及制备水泥时高污染、高能耗及高成本等问题,采用固体硅酸钠(Na_(2)O·SiO_(2),简称NS)激发双先驱剂(粉煤灰(fly ash),简称FA)和磨细高炉矿渣(ground granulated blast furnace slag,简称GGBFS)制备一步法地质聚合物浆料(one-partgeopolymer,简称OPG)。研究FA掺量、NS摩尔数、碱激发剂浓度、水灰比等因素对地质聚合物浆料物理及力学性能的影响规律。在此基础上,开展优化配比试验,确定可作为土壤固化剂的地质聚合物最优配比。然后,将综合指标最优的地质聚合物配比用以固化软土。进一步研究双先驱剂中FA/GGBFS质量比和养护龄期对固化软土无侧限抗压强度(unconfined compressive strength,简称UCS)、孔隙率和孔径分布的影响。通过压汞法(mercury intrusion porosimetry,简称MIP)和扫描电子显微镜-能谱仪(scanning electron microscope-energy dispersive spectrometer,简称SEM-EDS)对试验进行微观分析,揭示其固化机制。研究结果表明:固体NS激发下的一步法地质聚合物能有效加固软土,其生成的水化凝胶物(N-A-S-H、C-A-H、C-S-H和C-A-S-H)能有效黏结土颗粒,从而促进形成致密固化土骨架。FA/GGBFS为0.1、水灰比为0.8、NS摩尔数为1.0、碱激发剂浓度为3 mol/L是固体硅酸钠激发的一步法地质聚合物固化软土的最佳配比,其固化软土的28 d无侧限抗压强度可达4.4 MPa,且具有良好的工作性。本研究扩展固体硅酸钠激发的一步法地质聚合物在深层搅拌技术中的应用,为软土地基的加固处理提供理论基础指导。

Tailored architecture of composite electrolyte for all-solid-state sodium batteries with superior rate performance and cycle life

Seeking for composite electrolytes reinforced all-solid-state sodium ion batteries with superior long lifespan and rate performance remains a great challenge.Here,a unique strategy to tailor the architecture of composite electrolyte via inserting polymer chains into a small quantity of sulfate sodium grafted C_(48)0H_(28)O_(32)Zr_(6)(UIOSNa)is proposed.The intimate contact between polymer segments and UIOSNa with limited pore size facilitates the anion immobilization of sodium salts and reduction of polymer crystallinity,thereby providing rapid ion conduction and reducing the adverse effect caused by the immigration of anions.The tNa+grafting of-SO_(3)Na groups on fillers allows the free movement of more sodium ions to further improve and ionic conductivity.Consequently,even with the low content of UIOSNa fillers,a high ionic conductivity of 6.62×10^(-4) S·cm^(-1) at 60℃ and a transference number of 0.67 for the special designed composite electrolyte are achieved.The assembled all-solid-state sodium cell exhibits a remarkable rate performance for 500 cycles with 95.96%capacity retention at a high current rate of 4 C.The corresponding pouch cell can stably work for 1000 cycles with 97.03%capacity retention at 1 C,which is superior to most of the reported composite electrolytes in the literature.

次亚磷酸钠分离-重铬酸钾滴定法测定钨尾矿中砷含量

选矿中产生的钨尾矿长期堆放,经过雨水冲刷,钨尾矿中的砷会进入到水土中,造成环境污染,准确测定钨尾矿中砷含量,有利于监测钨尾矿中砷对环境的污染程度。采用硝酸-氯酸钾饱和溶液和氟化铵溶液分解样品,再用硫酸溶液冒烟赶尽硝酸,在盐酸介质中,以硫酸铜为催化剂,用次亚磷酸钠将砷离子还原成元素态,析出的砷过滤分离,除去其他杂质。在硫酸溶液中,用过量的重铬酸钾标准溶液滴定溶解单质砷,过量的重铬酸钾以二苯胺磺酸钠为指示剂,用硫酸亚铁标准溶液返滴定。通过优化样品溶解条件和砷沉淀还原条件,建立了次亚磷酸钠分离-重铬酸钾容量法测定钨尾矿中砷含量的分析方法。通过测定滤液中的砷含量,考察了滤液中砷含量对砷测定结果的影响,可忽略不计,表明实验中砷沉淀完全。通过沉淀单质砷,过滤使砷与杂质元素分离,消除了杂质元素对砷测定的影响。运用重铬酸钾容量法测定3个钨尾矿样品中的砷,并进行加标回收实验,测定结果的相对标准偏差(RSD,n=11)在0.14%~2.1%,加标回收率在97.0%~101%。方法操作简单、精密度高,适合钨尾矿中高含量砷的测定,测定结果与碱融分离-碘量法结果基本一致。

钠离子存储器件中界面效应作用机制研究

可充电钠离子电池被视为下一代高效能二次电池的最佳候选之一。电池充放电过程中电极表面及电极与电解质界面行为均对其性能有较大依赖性。因此,分析界面效应的特性对打造高能量密度、长期稳定的大型储能系统至关重要。虽然电极材料的特性研究已相当深入,但对钠离子电池界面效应的稳定性和高效性的研究仍显不足。现有研究成果尚未能为系统性结论提供充分的理论依据。本文回顾了钠离子储存设备中界面效应机制的研究现状,涵盖了电极材料内部的异质界面和固态电解质界面,从理论上分析了层间插入、转化反应和合金化过程中的界面效应,以及这些效应如何影响电池的整体性能。本文旨在为优化电极材料内部的异质界面及固态电解质结构提供理论基础,以提高钠离子电池的性能。同时,本文总结了几种现有的界面效应机制,并综述了目前界面效应研究面临的挑战与机遇,对其在该领域的未来发展进行了展望。

多温下三元体系Li^(+),Na+∥Cl^(-)-H_(2)O固液相平衡研究

卤水体系中LiCl富集度较高,且高纯度LiCl在工业上有广泛的应用,因Na^(+)和Li^(+)的性质相似,除去卤水中的NaCl成为了生产高纯度LiCl的瓶颈。Li^(+),Na^(+)∥Cl^(-)-H_(2)O三元体系的固液相平衡数据是分离LiCl和NaCl必需的重要基础数据。采用等温溶解平衡法研究了常压下Li^(+),Na^(+)∥Cl^(-)-H_(2)O三元体系的固液相平衡关系(348.15、358.15、363.15 K)并构建等温平衡相图。结果表明,不同温度下的相图均由一个共饱点、两个单盐结晶区(NaCl和LiCl·H_(2)O)及两条单变量溶解度曲线构成,未形成复盐或固溶体。随着温度的升高,NaCl的结晶区略有扩大,而LiCl·H_(2)O的结晶区变化很小。LiCl对NaCl有较强的盐析作用。采用修正的BET模型对相平衡数据进行了关联,结果良好,验证了该模型适用于预测本体系在高温、高浓度下的相平衡关系。测量了该体系饱和溶液密度并由密度值计算了表观摩尔体积,结果表明,密度随LiCl组成的增加先减小后增大,在共饱点组成处达到最大值。这些结果补充了Li^(+),Na^(+)∥Cl^(-)-H_(2)O体系在高温下的热力学数据,对脱除Na^(+)精制LiCl起到基础性的指导作用。

NASICON型Na_(1+x)Zr_(2)Si_(x)P_(3-x)O_(12)固态电解质及其钠金属电池研究进展

锂离子电池由于具有较高的工作电压和能量密度实现了商业化。然而,有限的锂资源限制了其广泛应用。钠离子电池展现出与锂离子电池相似的电化学特性,并且钠盐资源更加丰富,因此受到了广泛关注。目前,钠离子电池使用的是有机电解液,这存在一系列安全隐患,如漏液和燃烧等,采用固态电解质可以有效解决这些问题。然而,电解质的离子电导率仍有待提升,且材料制备的一致性及与电极间的界面阻抗问题限制了其广泛应用。针对离子电导率的问题,总结分析了不同价态离子取代的影响。针对存在的界面问题,从正极、负极两侧分析了现有Na_(1+x)Zr_(2)Si_(x)P_(3-x)O_(12)电解质的界面改性方法。最后,对Na_(1+x)Zr_(2)Si_(x)P_(3-x)O_(12)电解质的发展方向进行了展望,有望推动固态钠离子电池的发展。

硝酸根添加剂提升钠金属电池循环稳定性

钠金属电池由于金属钠具有的高比能量密度和低电极电势特性极具发展潜力,然而,传统的碳酸酯类电解液与钠金属之间持续反应,导致电池的循环稳定性能不理想。添加剂策略是一种提升电解液性能的简单有效策略,通过盐包盐策略成功制备了NaNO_(3)作为添加剂的酯类电解液。DFT计算和NMR测试结果表明,NO_(3)^(-)将进入Na+溶剂化鞘层内侧,在钠金属负极优先还原。对于钠金属界面的SEM和XPS表征结果及电化学测试显示,NO_(3)^(-)的还原构建了含氮的SEI界面,助力均匀稳定的钠金属沉积剥离行为。Na_(3)V_(2)(PO_(4))_(3)(NVP)与钠金属负极组装的钠离子电池在NO_(3)^(-)改性的酯类电解液中可获得超长稳定循环,在2 C(1 C=110 mA/g)下循环了2000次后容量保持率高达89.9%,在5 C下循环1000次后容量保持率为97.4%。